C Thermal Oxidation

Oxidation -
National Chiao-Tung University

Department of Electronics Engineering &
Institute of electronics
1
Thermal Oxidation
Oxidation method
wet oxidation
dry oxidation
rapid thermal oxidation
high pressure oxidation
plasma enhanced oxidation
Oxide hardness technology
post oxidation anneal
nitrogen passivation
N
2
O or NO oxidation, N
2
O or NO anneal, nitrogen implantation
fluorine passivation
HF dip, VHF clean, NF
3
additive, fluorine implantation

Oxidation -

2
Atomic Structures
SiO
2
Density=2.26(2.4) g/cm
3
Oxidation -

3
Thermal Oxidation
Dry Oxidation
Si (s) + O
2
(g) SiO
2
(s)
Wet Oxidation
2H
2
(g) + O
2
(g) H
2
O (g)
Si (s) + H
2
O (g) SiO
2
(s) +2H
2
(g)
0.44d Si to 1d SiO
2
Oxidation -

4
Deal-Grove Model-1
Oxidants must be transported from the bulk of the gas to
the oxide surface.

C
g
: oxidant concentration in bulk of gas
C
s
: oxidant concentration right next to the oxide surface
h
g
: gas phase mass-transfer coefficient
Henrys law
In equilibrium, the concentration of a species within a solid is proportional
to the partial pressure of that species in the surrounding gas.
C=Hp, where H is the Henrys law constant and p is the gas pressure
C* = H p
g
(equilibrium concentration in bulk SiO
2
)
C
o
= H p
s
(equilibrium concentration at bulk gas/SiO
2
interface)

) (
1 s g g
C C h F =
HkT h h C C h F
p/kT C
g o
/ where , ) (
gas ideal For
*
1
= =
=
Oxidation -

5
Deal-Grove Model-2
Oxidants must diffuse across the oxide layer already
present.

D is the diffusitivity of oxidant in bulk oxide
C
i
is the oxidant concentration in bulk oxide
at the oxide/silicon interface
x
o
is the thickness of oxide layer already present
Oxidants must react at the
oxide/silicon interface

k
s
is the chemical surface-reaction rate constant
o
i o
x
C C
D F

=
2
i s
C k F =
3
Oxidation -

6
Deal-Grove Model-3
Steady state : F=F
1
=F
2
=F
3
h
k
C
C C k
C C C D
D
x k
h
k
C
D
x k
C
D
x k
h
k
C
C
s
o i
o i
o s s
o s
o
o s s
i
+
=

+ +
|
.
|
\
|
+
=
+ +
=
1
0 As
and 0 0 As
1
1
and
1
*
s
*
*
*
Diffusion control
Reaction control
Oxidation -

7
Deal-Grove Model-4
N : The number of oxidant molecules incorporated into a
unit volume of oxide.
O
2
oxidation : N=2.2x10
22
molecules/cm
3
H
2
O oxidation : N=4.4x10
22
molecules/cm
3
( )
( )
B
Ax x
N
DC
B
h k
D A
t B Ax x
x x
D
x k
h
k
C k
F
dt
dx
N
i i
s
o o
i o
o s s
s o
+
|
|
.
|
\
|
+
+ = +
=
+ +
= =
2
*
2
*
2
1 1
2
0 condition initial ,
1
t
t
Oxidation -

8
Deal-Grove Model-5
( )
( )
( )
constant rate linear the is
ip relationsh linear called is t
4
t As
constant rate parabolic the is
ip relationsh parabolic called is
4
As
1
4
1
2
From
*
2
2
2
2
2

N
C
h k
h k
A
B
A
B
x
B
A
B
Bt x
B
A
t
B
A
t
A
x
t B Ax x
s
s
o
o
o
o o
+
=
+ =
<< +
=
>>
+
+ =
+ = +
t
t
t
t
Reaction control Diffusion control
Oxidation -

9
Initial Oxidation
Massouds experimental model:

Apply to either (111) or (100) oriented Si.
The first term is the Deal-Grove Model.
The second term represents an additional oxidation mechanism.
The actual mechanism is still not clear.
nm L eV E hr m C
kT
E
C C
L
x
C
A x
B
dt
dx
A o
A
o
o
o
o
7 and , 35 . 2 , / 10 6 . 3
exp
exp
2
8
~ ~ ~
|
.
|
\
|
=
|
.
|
\
|
+
+
=
Oxidation -

10
Oxidation Equipments
Furnace oxidation
(Hot wall)
Rapid thermal oxidation
(Cold wall)
Oxidation -

11
Oxidation Furnaces
Oxidation -

12
Oxidation Recipe

Oxidation -

13
Measurement of Oxide
Color chart
Physical methods
Scanning Electron Microscope (SEM), Transmission Electron Microscope
(TEM), Surface Profiler, Atomic Force Microscope (AFM)
Detect : thickness, interface structure, surface roughness
Optical methods
Ellipsometer
Detect : thickness (T), refraction index (n), absorption index (k)
Electrical methods
Capacitance-Voltage curve, electrical strength, interface state density, etc.
Oxidation -

14
Color Chart
Oxidation -

15
Scanning Electron Microscopy
Principle :
image contrast obtained by electron from different material or different
topography
Signal to Form Images :
Secondary Electron (SE)
E
e
<50 eV, escaping depth < 10 nm
backscattered electrons (BE)
E
e
~ E
b
electron channeling (EC)
electron beam induced current/voltage (EBIC/EBIV)
x-ray
characteristic x-ray of elements
cathodoluminescence (CL)
photon generated by e-h recombination
specimen current
Oxidation -

16
Transmission Electron Microscopy
Principle :
image contrast obtained by electron transmitted through thin materials
Signal to Form Images :
bright field image
direct transmitted beam to provide micro-structure and morphology
dark field image
diffracted beam image to obtain crystallographic information
lattice image (high resolution TEM, HREM)
a combination of diffracted and direct beams to yield images with atomic resolution
diffraction
diffraction yields crystallographic and orientation information
x-ray spectroscopy (EDX/WDX)
electron energy loss spectroscopy (EELS)
energy analysis of transmitted electron to analyze low-Z element
Oxidation -

17
TEM Sample Preparation
Plane-View Sample
circular sample cut to diameter 3mm
chemical or mechanical thinning to 100 um
chemical or ion-milling to form ultra-thin area

Cross-Sectional Sample
rectangular sample cut to 2mm x 3 mm
stack samples
mechanical polish to 20 um
fixed by Cu-ring
ion-milling to form ultra thin area
Precision Sample
FIB cut
3 mm
ultra thin area
3 mm
2 mm
E-beam
Oxidation -

18
SiO
2
/Si Interface
Si Lattice
Image
SiO
2
Oxidation -

19
Atomic Force Microscopy
Principle :
a sharp tip is vibrated perpendicular to the sample surface at the resonant
frequency.
Van der Waals force between probe tip and sample surface modify the
resonant frequency.
The change of resonance provides a corresponding displacement.
Application :
surface morphology measurement
sensitivity ~ atomic level
three dimensional topography measurement
accuracy +-1 nm, repeatability +-10 nm

Oxidation -

20
Ellipsometer
layer ith the of thickness the t
layer ith the of index absorption the k
layer ith the of index refraction the n
air of index refraction the n
1 all with ) , , , , , , ,
1 all with ) , , , , , , ,
. measurable are
) 360 0 ( and ) 90 0 ( angles ric ellipsomet The
) tan( ratio reflection complex The
) (
) (
;
(
) (
i
i
i
o
> = A
> =
A u
u = =
= =
A
i k n t k n n f (
i k n t k n n f (
e
R
R
Incident E
relected E
R
incident E
ref lected E
R
s s i i i o
s s i i i o
j
s
p
s
s
s
p
p
p
|
|
Oxidation -

21
Spectrum Ellipsometer
Oxidation -

22
Effect of Oxidation Ambient
Wet oxidation rate is much higher than dry oxidation rate
because the oxidant solubility in SiO
2
(C
*
) is much higher
for H
2
O than for O
2
.

Oxidation -

23
Effect of Crystal Orientation
Dry O
2
/1000C/1hr
Effect of crystal orientation is explained by the differences
in the surface density of silicon atoms on the various
crystal faces.
Oxidation -

24
Effect of Pressure
The concentration of oxidant just inside the oxide at the
gas/SiO
2
interface C
*
is proportional to p
g
, then both B and
B/A are proportional to p
g
.
Oxidation -

25
Boron-doped
Effect of Impurity Concentration
The mechanism associates with the faster oxidation at the
Si/SiO
2
interface due to higher vacancy concentration, i.e.
B/A is affected.
The differences of oxidation time is more pronounced for n
+
Si than for p
+

Si and is more pronounced for low temperature oxidation compared to
high-temperature oxidations.
Phosphorus-doped
Oxidation -

26
Chlorine Incorporation
O
2
+ HCl or TCA or DCE
Effective for dry oxidation only
Lower interface state density
Lower defect density
Gettering of metal ions in oxides
Enhanced oxidation rate due to
Rough interface at high Cl concentration (TCA>8%)
O H Cl O HCl
2 2 2
2 4 + +
Oxidation -

27
Fluorine Incorporation
Methods
HF surface immersion
F
2
surface treatment
Oxidation with NF
3
additive
F+ implantation into Si or oxide
Fluorine effects
Enhanced oxidation rate
Lower dielectric constant
Better oxide quality
Enhanced boron penetration
Poorer dielectric reliability with excess fluorine

Oxidation -

28
Nitrogen Incorporation
Higher low field mobility
Lower high field mobility
Lower defect density
Higher reliability
Stronger radiation immunity
Slower boron penetration

Oxidation -

29
Nitrogen Incorporation
Oxidation -

30
Oxide Charges
Flat-band voltage (V
fb
) and threshold voltage (V
th
)
( )
F
ox
Si
fb th
T
m
ox ox ox
f
ox
it
ox
ot
ms fb
C
Q
V V
dx x
T
x
C C
Q
C
Q
C
Q
V
ox
|
|
2
1
0
+ =
(
=
}
Oxidation -

31
Oxide Charges
Interface charge (Q
it
)
Magnitude depends on Si orientation : (111)>(110)>(100)
Magnitude depends on surface impurity and interface bonding
Magnitude can be reduced by annealing at 400-500
o
C in H
2
ambient
Fixed charge (Q
f
)
Immobile and independent of surface potential
Depends on Si orientation and oxidation condition
Oxidation -

32
Oxide Charges
Mobile ion (Q
m
)
Comes from metal contamination
Drift rate is thermally activated and is field dependent
Trapped charge (Q
ot
)
Maybe positive or negative
Maybe caused by ionization radiation or carrier injection
Trap site comes from defect in oxide layer
Low temperature annealing can not remove trap site but cause
neutralization or compensation of trapped charge.
Polarization charges (Q
p
)
Comes from electric field induced dipole

Oxidation -

33
Effect of Mobile Ions
SiO2
HfO2
EOT 1
Q(x)
EOT
EOT 1
EOT 2
0
X
HfO2
SiO2
P-type
v
EOT
2
2
2 2
,
2
,
1
[ 1* *
1 1
1 * ( 1 )* ]
2 2
it S iO it High
Hig
FB ms
ox
S iO h
V EOT EOT
EOT EOT EOT
Q
Q
Q
Q
k
k
|
c

= +
+ +
0
1 1
( )
d
FB
o
V xQ x dx
C d
(
= }
(

- 12 -
Oxidation -

34
Application of Thermal Oxides
Oxidation -

35
ITRS Roadmap (2003)
Oxidation -

36
Carrier Injection
Tunneling Mechanism

Schottky Emission

Frenkel-Pool Emission

Fowler-Nordheim Tunneling
or Field Emission

Ionic Conduction

Space Charge Limited

Ohmic

Direct Tunneling
( )
|
|
.
|
\
|
+
(
(

=
kT
q
T
V a
T
kT
qE q
T A J
B I B
| tc |
exp ~
4 /
exp
2 2 *
( )
|
|
.
|
\
|
+
(
(

=
kT
q
T
V a
V
kT
qE q
E J
B I B
| tc | 2
exp ~
/
exp
( )
|
.
|
\
|
(
(
=
V
b
V
E q
q m
E J
B
exp ~
3
2 4
exp
2
2 / 3 *
2
|
|
.
|
\
|
A
=
T
c
T
V
kT
E
T
E
J
a
exp ~ exp
|
.
|
\
|
'
A
=
T
c
V
kT
E
E J
a
exp ~ exp
( ) | |
( )
(
(

=
2
3
2
3
2
3
2
2
1
2
exp
1
s
ox s s
ox
s ox s
ox
qV
E
C
qV
BE
J
|
| |
| |
2
3
2
~
4
V
L
V
J

t
c
, =
S.E.
F-P
F-N
D.T.
Ionic
Oxidation -

37
Issues of Thin Oxide
Direct tunneling current

Maximum tolerable I
gate
( )
( )
2
3 2
1
2
3
2
3
2
3
2
3
2
2
1
2
2
3
4
16
exp
1
s
ox
s
s
ox s s
ox
s
ox s
ox
DT
q
m
C
q
B
qV
E
C
qV
BE
J
|
| t
|
| |
|
|
=
=
(
(
(
(
|
|
.
|
\
|
=
( ) ( )
2
gate
/ 1
m 0.1 / / 1
m 0.1 L As
/ 1
cm A
m nA I
m nA I I
gate
off gate
=
=
=
~ <

1um
0.1 um
Oxidation -

38
Poly-Si depletion

Influence
Constant field & constant N
poly

=> constant V
poly
An 0.3-0.5nm thick EOT loss is
inevitable.
poly Si
g ox
acc ox inv ox
poly
Si
poly
poly ox Si fb g
N q
V
T T
N
Q
V
V V V V V
c
c
2
2
,
2
,
2
2
+ =
+ + + =
meas
o ox
C
A
EOT
c c
=
Oxidation -

39
Quantum effect
Because of the conduction band triangular like well at the surface,
electron states are a series of discrete levels above the edge of the
conduction band.
The surface potential is larger than classical predicted.
Charge is located 0.5-1.0 nm away from surface than classical predicted.
Consequences
A 0.3 nm increase of effective oxide thickness
An increased depletion layer charge density
Oxidation -

40
Boron penetration
Boron may diffuse through gate oxide
from p+ poly-Si gate of PMOSFET.
Positive flat-band voltage shift
Degradation of oxide wearout properties
Thinner oxides result in severer boron
penetration effect.
Fluorine and hydrogen enhance boron
diffusion.
Crystallized a-Si retards boron diffusion.
Nitrided oxides reduce boron diffusitivity.
Trade-off between boron
penetration and poly depletion
Tox=3.3nm
IEDM, 1995, p.85
VLSI-TSA, 1997, p.167
Oxidation -

41
Advantages of High K Dielectric
Thicker thickness

Lower EOT
Lower tunneling current
ox
ox
HK
HK
T T
c
c
=
Oxidation -

42
Requirement of High K Dielectric
Criteria

Requirement

EOT scalability < 1 nm

Dielectric constant > 15

Negligible FIBL effect

Dielectric constant < 60

Leakage current < 1A/cm
2
Band gap > 5eV
Barrier height > 1eV
Thermal stability

No silicidation and reduction

Hysteresis

< 20mV

Dispersion

<1% /dec

Interface state density

<10
11
1/eV/cm
2

Mobility

>85% of SiO
2

Reliability

> 10 years

Oxidation -

43
Band Alignment Consideration
Energy gap of dielectric depends on dielectric constant.
Oxide

Dielectric
Constant

SiO
2

3.9

Si
3
N
4

7-9

HfO
2

~30

ZrO
2

~25

Al
2
O
3

9-13

Y
2
O
3

11-17

Ta
2
O
5

25-45

La
2
O
3

21

C Thermal Oxidation

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Oxidation -

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