Professional Documents
Culture Documents
Lecture 12
Mechanisms of Oxidation and Corrosion
12.1 Surface and Interface reactions in oxidation of metals
- thermal oxidation
12.2 Thermal oxidation of Si: Deal-Grove
12.3 Diffusion in metal oxide thin films
12.4 Corrosion (anodic oxidation)
- thermodynamics
- kinetics
References:
1) Zangwill, p.104-109
2) S.A. Campbell, The Science and Engineering of Microelectronic Fabrication, 1995
3) B. E. Deal and A. S. Grove, J. Appl. Phys., 36 (1965) 3770
4) C.Y. Chang, S.M. Sze, VLSI Technology, McGraw Hill
1
When cations diffuse, the initially formed oxide drifts towards the metal
When anions diffuse, the oxide drifts in the opposite direction
2
Lecture 12
Physics 9826b
Kirkendall effect
Marker at the diffusion interface move slightly in the opposite direction to the
most rapidly moving species vacancies can move!
Lecture 12
Physics 9826b
Cabrera-Mott theory
Lecture 12
Physics 9826b
During the oxidation of different metals, various empirical rate laws have
been observed
Linear law: w = kL t
w weight gain
per unit area; or
oxide thickness
Lecture 12
Physics 9826b
Oxidation of metals
Protective oxide films:
1. The volume ratio of oxide to metal after oxidation should be close to 1:1
or Pilling-Bedworth ratio = 1 (ration of oxide volume produced by oxidation to the volume
of metal consumed by oxidation)
10
Lecture 12
Physics 9826b
http://www.cleanroom.byu.edu/OxideThickCalc.phtml
11
Lecture 12
Si wafer
Linear
Si wafer
Parabolic
Si wafer
Physics 9826b
SiO2
Si
c0
csurf
ci
F1
F2
F3
xo
Depth (x)
Deal-Grove model
Recall: from ideal gas law, Cg=pg /kT
Henrys law: C0=H ps
F1 = h(C*-C0), where h=hg/HkT
F2 = D(O2) [(C0-Ci)/x0] (from Ficks law)
If we let rate at interface be proportional to concentration of oxidant at the SiO 2/Si
interface, then:
F2 = ksCi
Assuming steady state approximation: F1 = F2 = F3
h(C*-C0) = D(O2) [(C0-Ci)/x0] = ks Ci
algebra then, solve for concentration at the interface
C
Ci
1
kS
h
k S x0
D
; Co
k x
*
C 1 S 0
D
kS
k S x0
1
h
D
Lecture 12
14
Physics 9826b
dx
F3
dt
dt
F3
Hk
pg
k
k x
N 1 s s o
h
D
for x 0 x ( t 0 ) solution
x 0 Ax
2
1
1
A 2D
h
ks
For very t
x0
x 0 Ax
2 DC *
; B
;
N
B
hin oxides,
(t )
we can neglect
linear
quadratic
term,
and we have :
regime
For thick
oxides
x o B (t )
2
is
B (t )
parabolic
regime
15
Deal-Grove Model
Physical significance of 2 regimes:
- in linear regime for thin films, the
oxidant concentration is
assumed constant throughout
the system, C0 ~ Ci, rate is
controlled by interface (surface)
reaction;
- in the parabolic (thick film)
regime, Ci 0, and C0 ~ C* ;
and
B D, and diffusion through the
oxide dominates growth
kinetics
16
Lecture 12
Physics 9826b
17
Lecture 12
18
Physics 9826b
oxide
O2
substrate
Exchange
Oxide growth
19
16O
H+
18O
marker
tracer
(first)
(last)
Oxygen lattice
transport (O or
vacancy exchange)
Direct oxygen
transport (no Oexchange) to
interface
Energy
Concentration vs
depth
Lecture 12
10
Physics 9826b
A: To study processes,
not just structures!!
900 C
1.
18O
16O
4.
16O
800 C
movement at the
interface!
21
Gusev, Lu, Gustafsson, Garfunkel, PRB 52, 1759 (1995)
SiOx
Si (crystalline)
Lecture 12
22
11
Physics 9826b
No O-exchange
in bulk of oxide
SiO2 growth +
O-exchange
at interface
O2 decomp.
at surface
O-diffusion and
exchange in bulk
of oxide
Si-substrate
O2
O2
MOx growth,
O-exchange
at interface
Substrate
MOx
SiO2 films:
amorphous after annealing
molecular O2 transport in SiO2
decomposition by SiO desorption
(Many) transition metal and lantinide films:
tend to crystallize at low T
high oxygen mobility
23
ZrO2 /Si(001)
As deposited
5 nm
5 n m
3042513A-12, HAADF-STEM
Lecture 12
24
12
Physics 9826b
25
Lecture 12
26
13
Physics 9826b
18O
27
Dv= 2.5x10-7m2/s;
Db= 3.3x10-5m2/s;
28
Lecture 12
14
Physics 9826b
29
12.4 Corrosion
Corrosion is the deterioration of a material resulting from chemical reaction with
its environment
- temperature, pressure
- concentration of the reactions and products
- mechanical stress and erosion
Can be regarded as reverse extractive metallurgy
Metallurgy,
reduction
Metal
Corrosion,
oxidation
Spontaneous process
Lecture 12
15
Physics 9826b
1. Oxidation reaction: metals form ions that go into aqueous solution, also
called the anodic reaction; electrons are produced and remain in the metal
2. Reduction reaction: metals or nonmetals consume electrons and they are
reduced into zero-charge state, also called the cathodic reaction
Both oxidation and reduction reactions must occur at the same time
31
32
Lecture 12
16
Physics 9826b
33
Galvanic cells
Eo = +0.337 V
Overall reaction:
Zn + Cu2+ Zn2+ + Cu
Ecello = - 1.100 V
0 . 0592
n
where
log C ion ,
C ion is molar
concentrat
ion of ions
34
Lecture 12
17
Physics 9826b
Eo = -0.440 V
Cu Cu2+ + 2e-
Eo = +0.337 V
If acidic:
2H+ + 2e- H2
35
36
Lecture 12
18
Physics 9826b
37
38
Lecture 12
19
Physics 9826b
ItM
nF
where
iAtM
w is weight
I curretn
flow,
n number
i curretn
nF
of corroded
A; M atomic
of electrons
density,
or electropla
A/cm
produced
2
ted metal
; A area of electrode,
in time
t;
g/mol;
F 96500C/mol
cm
Acceleration of Corrosion
Physical Characteristics
exposed area (less, increases corrosion rate)
time of exposure (more time, more corrosion)
Environmental Characteristics
acidic environment
sulfur gas environment
temperature (high temps, more corrosion)
moisture (oxygenated moisture)
40
Lecture 12
20
Physics 9826b
Passivation
A protective film in oxidizing atmospheres
chromium,nickel, titanium, aluminum
41
Corrosion Prevention
Coatings
Barrier films
Inhibitive pigments
Sacrificial treatments
Paint
Active cathodic protection
42
Lecture 12
21