Pattern Transfer: Additive techniques-Physical

Vapor Deposition and Chemical Vapor Deposition

Dr. Marc Madou, Winter 2011
UCI Class 6
Content
Physical vapor deposition
(PVD)
Thermal evaporation
Sputtering
Evaporation and sputtering
compared
MBE
Laser sputtering
Ion Plating
Cluster-Beam

Chemical vapor deposition
(CVD)
Reaction mechanisms
Step coverage
CVD overview
Epitaxy
Electrochemical Deposition
Physical vapor deposition (PVD)
The physical vapor deposition technique is based on the formation of vapor of
the material to be deposited as a thin film. The material in solid form is either
heated until evaporation (thermal evaporation) or sputtered by ions
(sputtering). In the last case, ions are generated by a plasma discharge usually
within an inert gas (argon). It is also possible to bombard the sample with an
ion beam from an external ion source. This allows to vary the energy and
intensity of ions reaching the target surface.

Physical vapor deposition (PVD):
thermal evaporation
Heat Sources Advantages Disadvantages
Resistance No radiation Contamination
e-beam Low contamination Radiation
RF No radiation Contamination
Laser No radiation, low
contamination
Expensive
N = N
o
exp-
u
e
kT
6
The number of molecules
leaving a unit area of evaporant
per second
Physical vapor deposition (PVD): thermal
evaporation
K
n
= /D > 1
A ~ cos| cos u/d
2
N (molecules/unit area/unit time) =
3. 513. 10
22
P
v
(T)/ (MT)
1/2
The cosine law
This is the relation between vapor pressure of
the evaporant and the evaporation rate. If a high
vacuum is established, most molecules/atoms will reach
the substrate without intervening collisions. Atoms and
molecules flow through the orifice in a single straight
track,or we have free molecular flow :
The fraction of particles scattered by collisions
with atoms of residual gas is proportional to:
The source-to-wafer distance must be smaler than the mean free path (e.g, 25 to 70 cm)
Physical vapor deposition (PVD): thermal
evaporation
t
1
/t
2
=cos|
1
/cos|
2
= (tRT/2M)
1/2
q/P
T
From kinetic theory the mean free path relates
to the total pressure as:
Since the thickness of the deposited film, t, is proportional
to the cos |, the ratio of the film thickness shown in the
figure on the right with u = 0 is given as:

Physical vapor deposition (PVD): sputtering
W=
kV i
P
T
d
-V working voltage
- i discharge current
- d, anode-cathode distance
- P
T
, gas pressure
- k proportionality constant
Momentum transfer
Evaporation
and
sputtering:
comparison
Evaporation Sputtering
Rate Thousand atomic layers per second
(e.g. 0.5 m/min for Al)
One atomic layer per second
Choice of materials Limited Almost unlimited
Purity Better (no gas inclusions, very high
vacuum)
Possibility of incorporating
impurities (low-medium vacuum
range)
Substrate heating Very low Unless magnetron is used substrate
heating can be substantial
Surface damage Very low, with e-beam x-ray
damage is possible
Ionic bombardment damage
In-situ cleaning Not an option Easily done with a sputter etch
Alloy compositions,
stochiometry
Little or no control Alloy composition can be tightly
controlled
X-ray damage Only with e-beam evaporation Radiation and particle damage is
possible
Changes in source
material
Easy Expensive
Decomposition of
material
High Low
Scaling-up Difficult Good
Uniformity Difficult Easy over large areas
Capital Equipment Low cost More expensive
Number of
depositions
Only one deposition per charge Many depositions can be carried
out per target
Thickness control Not easy to control Several controls possible
Adhesion Often poor Excellent
Shadowing effect Large Small
Film properties (e. g.
grain size and step
coverage)
Difficult to control Control by bias, pressure,
substrate heat
Physical vapor deposition (PVD): MBE,
Laser Ablation
-
MBE
Epitaxy: homo-epitaxy
hetero-epitaxy
Very slow: 1m/hr
Very low pressure: 10
-11
Torr
Laser sputter deposition
Complex compounds (e.g.
HTSC, biocompatible
ceramics)
Physical vapor deposition (PVD): Ion cluster
plating
Ionized cluster: it is possible to
ionize atom clusters that are being
evaporated leading to a higher
energy and a film with better
properties (adherence, density,
etc.).
From 100 mbar (heater cell) to
10
-5
to 10
-7
mbar (vacuum)--
sudden cooling
Deposits nanoparticles
Combines evaporation with a
plasma
faster than sputtering
complex compositions
good adhesion

Gas cluster ions consist of many atoms or
molecules weakly bound to each other and
sharing a common electrical charge. As in the
case of monomer ions, beams of cluster ions
can propagate under vacuum and the energies of
the ions can be controlled using acceleration
voltages. A cluster ion has much larger mass
and momentum with lower energy per atom
than a monomer ion carrying the same total
energy. Upon impact on solid surfaces, cluster
ions depart all their energy to an extremely
shallow region of the surface. Cluster plating
material is forced sideways and produces highly
smooth surfaces.
Also individual atoms can be ionized and lead
to ion plating (see figure on the right, example
coating : very hard TiN)

Physical vapor deposition (PVD):Ion
cluster plating and ion plating


Chemical vapor deposition (CVD): reaction
mechanisms


Mass transport of the reactant in
the bulk
Gas-phase reactions
(homogeneous)
Mass transport to the surface
Adsorption on the surface
Surface reactions
(heterogeneous)
Surface migration
Incorporation of film
constituents, island formation
Desorption of by-products
Mass transport of by-produccts
in bulk
CVD: Diffusive-convective transport of
depositing species to a substrate
with many intermolecular
collisions-driven by a concentration
gradient
SiH4 SiH
4
Si
Chemical vapor deposition (CVD):
reaction mechanisms
Fl = D
Ac
Ax
o(x) =
qx
U
|
\

|
.
|
1
2
o =
1
L
o(x)dX =
2
3
0
L
}
L
q
UL
|
\

|
.
|
1
2
Re
L
=
UL
q
o =
2L
3 Re
L
Energy sources for deposition:
Thermal
Plasma
Laser
Photons
Deposition rate or film growth rate
(Ficks first law)
(gas viscosity q, gas density , gas stream velocity U)
(Dimensionless Reynolds number)
Laminar flow
L
o(x)
dx
(U)
(Boundary layer thickness)
Fl = D
Ac
2L
3 Re
L (by substitution in Ficks first law and Ax=o)
Mass flow controlled regime
(square root of gas
velocity)(e.g. AP CVD~ 100-10
kPa) : FASTER
Thermally activated regime:
rate limiting step is surface
reaction (e.g. LP CVD ~ 100
Pa----D is very large) :
SLOWER
Chemical vapor deposition (CVD)
: reaction mechanisms
Fl = D
Ac
2L
3 Re
L
R = R
o
e
-
E
a
kT
Chemical vapor deposition (CVD):
step coverage
Fl = D
Ac
2L
3 Re
L
R = R
o
e
-
E
a
kT
Step coverage, two factors are
important
Mean free path and surface
migration i.e. P and T
Mean free path: =



o
w
z
u=180
0
u=270
0
u=90
0
u is angle of arrival
kT
2
1
2
P
T
ta
2
> o
Fldu
}
u = arctan
w
z
Chemical vapor deposition (CVD) :
overview
CVD (thermal)
APCVD (atmospheric)
LPCVD (<10 Pa)
VLPCVD (<1.3 Pa)
PE CVD (plasma enhanced)
Photon-assisted CVD
Laser-assisted CVD
MOCVD
The L-CVD method is able to fabricate
continuous thin rods and fibres by pulling the
substrate away from the stationary laser focus
at the linear growth speed of the material while
keeping the laser focus on the rod tip, as shown
in the Figure . LCVD was first demonstrated
for carbon and silicon rods. However, fibers
were grown from other substrates including
silicon, carbon, boron, oxides, nitrides,
carbides, borides, and metals such as
aluminium. The L-CVD process can operate at
low and high chamber pressures. The growth
rate is normally less than 100 m/s at low
chamber pressure (<<1 bar). At high chamber
pressure (>1 bar), high growth rate (>1.1
mm/s) has been achieved for small-diameter (<
20 m) amorphous boron fibers.


Chemical vapor deposition (CVD) : L-CVD
Epitaxy
VPE:
MBE (PVD) (see above)
MOCVD (CVD) i.e.organo-metallic
CVD(e.g. trimethyl aluminum to
deposit Al) (see above)
Liquid phase epitaxy
Solid epitaxy: recrystallization of
amorphous material (e.g. poly-Si)
Liquid phase epitaxy
Epitaxy
Selective epitaxy
Epi-layer thickness:
IR
Capacitance,Voltage
Profilometry
Tapered groove
Angle-lap and stain
Weighing
Selective epitaxy
Electrochemical deposition: electroless
Electroless metal displacement
Electroless sustainable oxidation of a
reductant
Metal salt (e.g.NiCl
2
)
Reductant (e.g.hypophosphite)
Stabilizer:bath is
thermodynamically unstable needs
catalytic poison (e.g. thiourea)
Complexing agent : prevent too
much free metal
Buffer: keep the pH range narrow
Accelerators: increase deposition
rate without causing bath
instability (e.g. pyridine)

Deposition on insulators (e.g. plastics): seed
surface with SnCl
2
/HCl
1. Zn(s) + Cu
2+
(aq) ------> Zn
2+
(aq) + Cu(s)



2. Reduction (cathode reaction) :
Ni
+2
+ 2e
-
> Ni
Oxidation (anode reaction):
H
2
PO
2-
+ H
2
O> H
2
PO
3
-
+2H
+
+2e
-
-------------
-----------------------------
Ni
+2
+ H
2
PO
2
-
+ H
2
O > Ni + H
2
PO
3
-
+ 2H
+

e.g. electroless Cu: 40 mhr
-1
Cu
Electrochemical deposition: electroless
Evans diagram: electroless deposition is
the combined result of two independent
electrode reactions (anodic and cathodic
partial reactions)
Mixed potential (E
M
): reactions belong to
different systems
i
deposition
= i
a
= i
c
and I=A x i
deposition

Total amount deposited: m
max
= I t M/Fz (t
is deposition time, Molecular weight, F is
the Faraday constant, z is the charge on the
ion)
CMOS compatible: no leads required


Evans diagram
F= 96,500 coulombs=1, 6 10
-19
(electron charge) x 6. 02 10
23
(Avogadros number)
+
-
Electrochemical deposition :electrodeposition-
thermodynamics



Electrolytic cell
Au cathode (inert surface for Ni
deposition)
Graphite anode (not attacked by Cl
2
)
Two electrode cells (anode, cathode,
working and reference or counter electrode)
e.g. for potentiometric measurements
(voltage measurements)
Three electrode cells (working, reference
and counter electrode) e.g. for
amperometric measurements (current
measurements)
Electrochemical deposition
:electrodeposition-thermodynamics (E)
E = E
0
+
RT
zF
ln a
M
z +
G= G
2
- G
1
G=-(E
2
-E
1
)zF=-E
cell
zF
G= G
0
-RT ln a
M
z+
= G
0
-RT ln C
M
z+

M
z+
G= - EzF
E
2
> E
1
: - battery

E
2
< E
1
: + E
ext
> E
cell
to afford deposition

(Nernst equation)
1. Free energy change for ion in the solution to atom in the metal (cathodic reaction):

or also
2. The electrical work, w, performed in electrodeposition
at constant pressure and constant temperature:

and since AV =0
AG =G
m
(free energy pure metal)- G
e
(free energy of ion in the electrolyte)
AG = - w +PAV
3. Substituting Equation (2) in (1) one gets

(1)
(2)
4. Repeat (1) and (2) for anodic reaction:
or
Electrochemical deposition
:electrodeposition-thermodynamics (q)
A thermodynamic possible reaction
may not occur if the kinetics are
not favorable
Kinetics express themselves
through all types of overpotentials
E -E
o
= q ( + anodic and - is
cathodic)

G* = G
#
+|uA|
k
c

=
kT
h
e

AG
#
_
RT
k

= k

c
kT
h
e

|FA|
RT
i

= k

z F = k

c
z F
kT
h
e

|FA|
RT
i

= k

zF = k
c

z F
kT
h
e
(1 |)FA|
RT
Electrochemical deposition :electrodeposition-
kinetics-activation control
Understanding of polarization
curves: consider a positive ion
transported from solution to the
electrode
Successful ion jump frequency is
given by the Boltzmann
distribution theory (h is Planck
constant):
(without field)
(with field)
Electrochemical deposition :electrodeposition-
kinetics-activation control
i
e
= i

= k

c
zF
kT
h
e
(1 |)FA|
e
RT
= i

= i

c
zF
kT
h
e
|FA|
e
RT
q=A|A|
e
i = i

i = i
e
(e
(1|)Fq
RT
e
|Fq
RT
)
q= a + blog(i)
(Butler-Volmer)
(Tafel law)
At equilibrium the exchange current
density is given by:




The reaction polarization is then given
by:


The measurable current density is then
given by:


For large enough overpotential:
Electrochemical deposition :electrodeposition-
kinetics-diffusion control
dC
dX
=
C
x=
0
C
x=0
o
q
c
=
RT
nF
ln
C
x=0
C

0
i = nFD
0
C

0
C
x=0
o
I
l
= nFAD
0
C

0
o
i = i
l
(1 e
nFq
c
RT
)
From activation control to diffusion
control:


Concentration difference leads to
another overpotential i.e. concentration
polarization:



Using Faradays law we may write
also:


At a certain potential C
x=0
=0 and then:
C
x=0
C

0
=
1- i
i
l
we get :
Electrochemical deposition :electrodeposition-
non-linear diffusion effects
o = tD
0
t
( )
1
2
I
l
= nFAC

0
D
0
tt
|
\

|
.
|
1
2
I
l
= nFAC

0
D
0
tt
|
\

|
.
|
1
2
+ AnFD
0
C

0
r

Nonlinear diffusion and the advantages of using
micro-electrodes:


An electrode with a size comparable to the thickness
of the diffusion layer


The Cottrell equation is the current-vs.-time on an
electrode after a potential step:


For micro-electrodes it needs correction :
I
l
= nFAD
0
C

0
o
Electrochemical deposition :electrodeposition-
non-linear diffusion effects
I
l,m
= trnFD
0
C

0
(disc)
I
l,m
= 2trnFD
0
C

0
(hemisphere)
I
l,m
= 4trnFD
0
C

0
(sphere)
I
l,m
= AnFD
0
C

0
r + L
The diffusion limited currents for
some different electrode shapes are
given as (at longer times after bias
application and for small
electrodes):




If the electrodes are recessed
another correction term must be
introduced:
Homework
Homework: demonstrate equality of = (tRT/2M)
1/2
q/P
T
and = kT/2
1/2
a
2
t P
T

(where a is the molecular diameter)
What is the mean free path (MFP)? How can you increase the MFP in a vacuum
chamber? For metal deposition in an evaporation system, compare the distance
between target and evaporation source with working MFP. Which one has the
smaller dimension? 1 atmosphere pressure = ____ mm Hg =___ torr. What are the
physical dimensions of impingement rate?
Why is sputter deposition so much slower than evaporation deposition? Make a
detailed comparison of the two deposition methods.
Develop the principal equation for the material flux to a substrate in a CVD process,
and indicate how one moves from a mass transport limited to reaction-rate limited
regime. Explain why in one case wafers can be stacked close and vertically while in
the other a horizontal stacking is preferred.
Describe step coverage with CVD processes. Explain how gas pressure and surface
temperature may influence these different profiles.