Substrate Surfaces &

Thin-Film Nucleation
Basic modes of thin-film growth
Thermodynamics of
Thin-Film Nucleation
Thermodynamics of
Thin-Film Nucleation
Issues addressed:
conditions for stability of thin-film
role of surface energies
energies involved in nuclei formation
thermodynamics of different modes
influence of deposition rate & T
Issues addressed:
conditions for stability of thin-film
role of surface energies
energies involved in nuclei formation
thermodynamics of different modes
influence of deposition rate & T
Thermodynamics of Thin-Film Nucleation
r

sv

fv

fs
nucleus
d
e
p
o
s
i
t
i
o
n
d
e
s
o
r
p
t
i
o
n
substrate

cos
f f sv v s
+
) ( sin ) cos - (1 2
) cos cos 3 2 (
3

) (
sv fs
2 2
fv
2
V
3 3


+ +
+ +
r r
G r r G
V
S
fs
S
fv
~ 0.2 3 J/m
2
ignore
Thermodynamics of Thin-Film Nucleation
) ( sin ) cos - (1 2
) cos cos 3 2 (
3

) (
sv fs
2 2
fv
2
V
3 3


+ +
+ +
r r
G r r G
V
S
fs
S
fv
aturation) s uper s ( 1
) 1 ln( ln
S
V
B
V
S B
V

+

P
P
ss
ss
T k
P
P T k
G
If ss=0 G
V
= 0 and nucleation impossible
V
sv fs fs fv fv
3
)) ( ( 2
*
0 ) (
d
d
G V
S S
r
r G
r

( )

,
`

.
| +

4
cos cos 3 2
3
16
*) ( *
3
2
V
3
fv

G
r G G
G
V
r
r*
G*
wetting factor

,
`

.
|


T k
G
n N
B
S
*
exp *
density of stable nuclei:
n
S
- density of all nuclei
Thermodynamics of Thin-Film Nucleation
o
90 ;
fs fv sv
> + <
metals on dielectrics
fv
fs sv
cos

no wetting
wetting
( )
o
90 ;
fs fv sv
< +

'

'

>

autoepitaxy:
fs
=0
In general, materials with low surface energy
will wet substrates with a higher surface energy
misfit
Thermodynamics of Thin-Film Nucleation
e
R
R T k
G
&
&
ln
B
V

equilib. evap. rate from the nucleus at
the substr.T
K
3

6
V
,
2 2 3 10
V
sv fs fs fv fv
J/m 10 8 /
mJ/m 05 . 0 /
fv
, J/m 1
fv
, J/m 10 6 . 1
V
for
0
3
)) ( ( 2 *

<<
>

,
`

.
|

T G
T G
G V
S S
T T
r
R


&
Dependence on Substrate T and Deposition rate
V
P R
&
0
* * *
B
V
V
V
<

,
`

.
|

,
`

.
|

R
T k
G
r
R
G
G
r
R
r
T
& & &
0
*
<

T
R
G
&
0
*
<

R
T
G
&
Cu films on (111) NaCl
Zoo of adatomsfate
Kinetics of Thin-Film Nucleation
Issues addressed:
nucleation rate and its dependence on
t, T, , film itself and substrate
development of film growth and coalescence of nuclei
t-dep. of the growth and coalescence of nuclei
binding (good):
physisorption:
van der Waals (weak, 0.01eV)
chemisorption:
chemical bonds (strong, 1-10eV)
defects of
substrate
reflection (bad)
homogeneous
nucleation
heterogeneous
nucleation
(preferred)
desorption (bad)
hopping & diffusion
(initial growth)

,
`

.
|

T k
E
a D
B
diff
2
0 S
exp ~
Kinetics of Thin-Film Nucleation
diffusionis determined by:
E
diff
energy barrier for diffusion
T
s
temperature of substrate
vibrational frequency of an adatom
(attempt frequency)

,
`

.
|

T k
E
B
diff
J
exp frequency of surface jumps
X
cluster can be formed in overlap region
surface diffusion coefficient

,
`

.
|

T k
E E
a D X
B
diff des
0 S S
2
exp ~
~a
0
Kinetics of Thin-Film Nucleation
desorptionis determined by:
E
des
energy barrier for desorption
T
s
temperature of substrate
vibrational frequency of an adatom
(attempt frequency)

,
`

.
|

T k
E
B
des
S
exp
1

lifetime of desorbing adatoms

Kinetics of Thin-Film Nucleation
Nucleation rate
) s (cm * *
2 -
A N N
&
critical area
impingement rate onto nucleus
equilibrium concentration
of stable nuclei

,
`

.
|

RT
Mv
RT
M
v
n
n
v f
x
x
x
x
2
exp
2 d
d 1
) (
2
Maxwell- Boltzmann
RMT
PN
M
RT
n v
RT
Mv
v
RT
M
n v v f n n v
x
x
x x x x x
2 2
d
2
exp
2
d ) ( d
A
2
0 0 0

,
`

.
|

,
`

.
|

T k
G
n N
B
S
*
exp *
RT
N
n
P
A

the perfect gas law

~
X
r*sin
a
0
( )
0
sin * 2 * a r A

,
`

.
|

T k
E
B
diff
J
exp
J S

(absorption flux from vapor)

,
`

.
|

T k
E
B
des
S
exp
1

( )

,
`

.
|

T k
G E E
n
RMT
PN
a r N
B
diff des A
0
*
exp
2
sin * 2
&
Kinetics of Thin-Film Nucleation
Atomistic Nucleation Model

,
`

.
|
+
*
*
1
B
* *
ln
i
i
i i
N
N
T k E G
Critical free energy to form nucleus ("molecule")
(chemical equilibrium between clusters and monomers)
~
X
r*sin
a
0

,
`

.
|

T k
E
B
diff
J
exp

,
`

.
|

T k
E
B
des
S
exp
1

Walton-Rhodin Theory
treats clusters of atoms as molecules rather than solid caps
considers the bonds between atoms
is similar to the capillarity model
E
i*
- energy to break/form a critical cluster of i* atoms
N
i*
- density of critical nuclei
N
1
density of single adatoms
n
0
density of adsorption cites
"Chemical" reaction: iA=A
i

,
`

.
|

T k
E R
R N
B
des
S 1
exp

&
&

,
`

.
|

T k
E E
a D X
B
diff des
0 S S
2
exp ~

,
`

.
|

T k
E E
a X R
B
diff des
2
0
2
exp
&

,
`

.
|
+ +

,
`

.
|

T k
E E E i
n
R
n a R N
i
i
i
B
* diff des
*
*
0
0
2
0 *
) 1 (
exp

&
& &
Law of Mass Action (Waage & Guldberg 1867)
aA + bB + ... xX + yY + ...
[forward rate] k
1
[A]
a
[B]
b ...
[reverse rate] k
-1
[X]
x
[Y]
y ...
in equilibrium, k
1
[A]
a
[B]
b ...
= k
-1
[X]
x
[Y]
y ...
H
2
+ I
2
2HI;
the direct reaction results from collision of H
2
and I
2
molecules =>
reaction rate is proportional to the number of such collisions;
the number of collisions is proportional to density of H
2
and I
2
;
the density is proportional to pressure =>
the reaction rate is proportional to the partial pressures of H
2
and I
2
:
k
1
P
H
2
P
I
2
similarly, the reverse reaction rate is proportional to the number of collisions
between HI molecules => the reaction rate is
k
-1
P
HI
2
in equilibrium k
1
P
H
2
P
I
2
= k
-1
P
HI
2
we define the constant of equilibrium as
K(T) = k
-1
/ k
1
= P
H
2
P
I
2
/ P
HI
2
G = G
0
+ RT lnK,
Kinetics of Thin-Film Nucleation
Atomistic Nucleation Model

,
`

.
|
+ +

,
`

.
|

T k
E E E i
n
R
n a R N
i
i
i
B
* diff des
*
*
0
0
2
0 *
) 1 (
exp

&
& &
(continued)

,
`

.
|
+

n
R
k
E E
T
&
ln
B
2 des
2 1
2 * 1 *

i i
N N
& &

,
`

.
|
+

2 1 B
2 des
0
exp
T k
E E
n R
&
Kinetics of Thin-Film Nucleation
Kinetic Nucleation Model

2
1 1 1
S
1
1
d
d
i
i i
N K N N K
N
R N
t
&
i i i i i
N N K N N K N
t
1 1 1 1
d
d

,
`

.
|

,
`

.
|

T k
E
n
R
An N
p
B 0
0 S
exp

&
Kinetics of Thin-Film Nucleation
Cluster Coalescence and Depletion
r
1

1
r
2
Mass transport
i i i
i i
i
i
i
i
r dr r
dr r
r d
r d
dn
dG

2
) 3 4 (
) 8 (
) 3 4 (
) 4 (
2
3
2
Ostwald rippening (large islands grow at
the expence of the smaller ones)
Sintering
Cluster migration
Grain size