Professor N Cheung, U.C.

Berkeley
Lecture 13 EE143 F2010
1
Chemical Vapor Deposition (CVD)
film
substrate
chemical reaction
source
More conformal deposition vs. PVD
step
t
t
(

higher temp
has higher surface
diffusion)
Shown here
is 100%
conformal
deposition
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
2
|
, ) | +
| + +
+ +
+
| + +
Z Y X
O H C SiO H OC Si
ate orthosilic ene tetraethyl 1EOS c
H SiO O SiH
H O P O PH
SiO O P glass silicate phospho PSG b
H SiO O SiH
SiO a
2 4 5 2
2 2 2 4
2 5 2 2
2 5 2
2 2 2 4
2
. : ) (
2
6 2 5 3 4
. : ) (
2
) (
gas 350
o
C-500
o
C
solid
350
o
C-500
o
C
gas
LPCVD Examples
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
3
| + +
+
-
+ +
Hl F H Fl
F /
H Si SiH
Si Poly e
H | Si |H SiH
| Si 1
C
o
6 3
) (
2
) (
!2 3
) (
2 6
2
6||
4
2 4 3 3 4
4 3
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
4
CVD Reactors
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
5
CVD Mechanisms
reactant
1
2
5
4 3
stagnant
gas layer
surface
diffusion
substrate
1 = Diffusion of reactant to surface
2 = Absorption of reactant to surface
3 = ChemicaI reaction
4 = Desorption of gas by-products
5 = Outdiffusion of by-product gas
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
6
Example: Poly-Si Deposition
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
Flux across boundary
Flux used in reaction
Normalize to total pressure
Thickness growth velocity
) C C ( h F
S G G 1
- =
S S 2
C k F - =
... P P
P
C
C
Y
2 _ GAS 1 _ GAS
GAS
SPECIES _ ALL
GAS
+ +
= =
N
F
v =
CVD Growth Rate ModeI
N = atomic density of film
7
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
Diffusion Constant in Gas
: F
n
1
v
4
-
n
2
v
4

v
4
(i
dn
dx
) where i mean Iree path oI gas collision.
F D
dn
dx
D
i v
2
Since i
kT
P
and v T
D T
3/2
/P
P
T
D D
2 / 3
o
- =
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
Mathematical Model for CVD (Cont.)
Transport parameter h
G
= D/
D = gas diffusion constant = D
o
-T
3/2
/ Pressure
Surface reaction parameter k
S
= k
o
exp (-E
a
/kT)
BaIancing F
1
=F
2
Growth velocity
C
ALL_SPECES
= concentration at top of boundary layer
N =atomic density of deposited material
Limiting cases
k
S
<< h
G
Surface Reaction limited
h
G
<< k
S
Mass Transport limited
Y
N
C
) h / 1 k / 1 (
1
N
F
v
SPECIES _ ALL
G S
+
= =
9
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
10
Deposition Rate versus Temp
[log scale] Rate
0
2
3
T
Mass transport limited
surface-reaction
limited
1/ T
low
T
high T
kT / E
A
c

Professor N Cheung, U.C. Berkeley

Lecture 13 EE143 F2010
11
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
Boundary Layer Thickness vs. Distance
2
!
) (
|
|
.
|

\
|
=
U
x
x
S

= viscosity, = density, U = veIocity

12
*See handout on CVD Kinetics for derivation
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
13
Average Boundary Layer thickness <o>

= - o >= o <
}
UL
L
3
2
dx ) x (
L
1
L
0
c

UL
=

is called the Reynold Number of the reactor. When Re is

small ( < 2000), gas flow is viscous. When Re is large
(>2000), gas flow is turbulent which is undesirable.
U
1
h
G

> o <

f deposition rate is mass transfer limited,
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
Growth Rate Dependence on FIow VeIocity
Y
N
C
) h / 1 k / 1 (
1
N
F
v
SPECIES _ ALL
G S
+
= =
Fixed temp T
14
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
15
LPCVD Reactors
(next page)
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
16
Example calculation:
P reduces ~1000X from 1 atmosphere to ~1 Torr
Velocity of gas flow U increases ~100X due to pumping
h
P
D Torr Torr From
G
300X
3
1000
3X
100
1000
1000X 1 760

~
|
P
D
1

U
velocity of gas flow 100X
D

Therefore, LPCVD is more likely

to be surface reaction Iimited
Gas density
LPCVD: Low Pressure and high gas velocity due to pumping
h
G
|
=
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
17
(1) R | , since h
G
|
(2) More conformal deposition,
if T is uniform
(3) nter-wafer and intra-wafer thickness uniformity less sensitive
to gas flow patterns. (i.e. wafer placement).
Wafer
topography
LPCVD Features
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
18
Gas Flow ssues
(2) Mass depletion problem
in
out
more less
(1) depends on gas flow pattern
Furnace tube
wafers
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
19
(1) Temperature Ramping along reactor length
For reaction - limited regime:
R(x) = A exp[-E
A
/kT] C(x) [where C(x) = SiH
4
Conc.]
Creating a temperature gradient of 20 - 40C along the
tube will give better uniformity.
(2) Distributed Feed Reactors
Solutions for mass depletion problem
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
20
PECVD Reactors
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
21
onized chemical species allows a lower process
temperature to be used.
Film properties (e.g. mechanical stress) can be tailored
by controllable ion bombardment with substrate bias voltage.
Plasma Enhanced CVD
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
22
Epitaxial Growth
Requires an ultra-clean Si surface prior to epi growth.
Requires deposition of Si at very high temperature for
perfect crystallinity.
Processing
Temperature
950-1150
o
C
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
23
Strained Si Growth by Heteroepitaxy
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
24
Self-limiting surface
reactions of suitable
precursor compounds
A and B, which form
the desired product S
in a binary reaction
cycle consisting of
two sequential
half-reactions.
PrincipIe of Atomic Layer Deposition
For an extensive list of precursors,
see Ritala and Leskela, Handook of Thin Film
Materials, Vol.1, Chap 2 (2002)
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
25
Timing Sequence : CVD vs ALD
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
26
SpatiaI ALD
Reaction Chamber A
Reaction Chamber B
The reactor has separate zones exposing the precursors one by one to a substrate that moves
underneath the reactor. Gas bearings between the zones eliminate cross-diffusion and
therefore the need for purge steps. Half-reaction timescales are ~10 msec, enabling ultrahigh
deposition rates while maintaining ALD film quality.
Source: PV Society, 2010
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
27
Possible Spatial ALD Configuration
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
28
ExampIe: ZrO2 ALD
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
29
Step Coverage
(Al2O3)
Professor N Cheung, U.C. Berkeley
Lecture 13 EE143 F2010
30
SUMMARY OF THIN FILM MODULE
Vacuum Basics Mean Free Path and mpingement Rate
Plasma Basics - A plasma sheath above electrode
surface which maintains a voltage drop ( -10 to - 1000V)
for ion bombardment
PVD and CVD
Evaporation Vapor Pressure
Sputtering Deposition- Sputtering Yield, Co-sputtering
PVD ssues thickness uniformity across wafer, Step
Coverage ( geometric shadowing , Self Shadowing)
CVD Deposition Rate ( h
G
versus k
s
effects)
CVD ssues Conformal coverage, Mass depletion
Plasma Enhanced CVD (PECVD) - qualitative
Epitaxial Growth - qualitative
Atomic Layer Deposition (ALD) - qualitative