ThinFilmDepositiontechniques

ThermalEvaporation

SCPY663 Sem2/2009 (Physics-MUSC)

An evaporator

Evaporator

SCPY663Sem2/2009(PhysicsMUSC)

Evaporation rate
all materials have an equilibrium vapor pressure, pe(T)
(T: source temperature)
att sufficiently
ffi i tl high
hi h ttemperature,
t
th
the gas iimpingement
i
t rate
t = (p
( e)
can be high enough to cause deposition of material (thin-film growth)
on a cold substrate (TS<<T, TS: substrate temperature)

cold substrate, Ts

vapor

T>> Ts
hot source, T

SCPY663 Sem2/2009 (PhysicsMUSC)

Evaporation rate
Gas impingement rate for thermal evaporation (Knudsen equation, Ch.2 p.8)

N ( p ph )
e = A e
2MRT

pe: equlibrium vapor pressure of the source

ph: hydeostatic pressure acting on the evaporant

Usually: ph = 0 (vacuum)

pe
pe
gK
gK
molecules
ML
22 torr
7 torr
= 3.5 10

3
.
5

10

cm 2 s
s
MT
MT

e = 5.8 10 2

M
K p
g

2
T
g torr cm s

1 ML 3

e: mass evaporation rate

typically 10-4 g/(cm2s)at 10-2 torr

!! pe = pe(T)
( ) !!
SCPY663 Sem2/2009 (PhysicsMUSC)

Clausius Clapeyron equation (solid liquid or liquid - vapor equlibrium)

dpe
H
=
dT T V

H: molar enthalpy difference

V: molar volume difference

V Vgas RT / p
dpe H (T )
=
pe
dT
RT 2
H(T) He molar
heat of evaporation

H
pe (T ) = p0 exp e
RT

Good approximation, but not exact (non perfect gas behavior, H(T) const.)
Water: He = 40.6
40 6 kJ/mol
5
p(373K) = 10 Pa - p(273K) = 103 Pa - p(77K) = 10-17 Pa
SCPY663 Sem2/2009 (PhysicsMUSC)

Clausius-Clapeyron equation only applicable if system is in equilibrium

((molar evaporation
p
and condensation rates,, Qv and Qc, are balanced))

orifice
ifi di
diameter
t <<
pe
evaporation rate
can be calculated

Qc Qv

q
Knudsen
cell

Qv

evaporation rate
must be measured

q
vacuum
evaporator

Rule of thumb: if pe(TM)10-3 torr then T >TM is required

SCPY663 Sem2/2009 (PhysicsMUSC)

Vapor pressure of selected elements

Al
Cu

1350K

SCPY663
melting
temperature Tm
Sem2/2009 (PhysicsMUSC)

Angular distribution of evaporants: cosine law

Emitting flux from any point on the surface; Jv
Total evaporation rate from a source of area A; Q = JvA
dAr
r

dAs

KQ
Q
r2
cosine flux distribution J = J 0 cos
F sphere
For
h off radius
di r; J 0 =

Receiving Flux on dAr ; J =

J 0 cos cos
dAr
2
r

K = geometry factor
=

K cell
K-cell

=
Jo

Jocos

1
4
1

; point source
; disc shape source e.g. boat

Deposition rate is determined in J=J cos2

In the typical case of disc-shaped source = ;
J = Jocos4 /r2
SCPY663 Sem2/2009 (PhysicsMUSC)

Evaporation of Compounds and Alloys

only very few compounds evaporate as molecules
vapor composition and film stoichiometry do not differ from that of
the
h source e.g. SiO
SiO, B2O3, GeO,
G O SnO,
S O AlN,
AlN C
CaF
F2, MgF
M F2)
most compounds decompose,
e.g.
(1) Ag2Se(s) 2Ag(g)+Se2(g)
((2)) SiO2((s)) SiO(g)+O
(g)
2(g)
evaporate from separate sources (1) or
introduce O2 partial pressure (2(2 reactive evaporation)
evaporated metal alloy films are widely used:
Al-Cu metallization in integrated circuits
Fe-Ni magnetic data storage
etc.
t
SCPY663 Sem2/2009 (PhysicsMUSC)

metal atoms in an alloy are less tightly bound than atoms in an inorganic compound
constituents nearly evaporate independently of each other,
enter vapor phase as single atoms
metallic melts are solutions and follow thermodynamics
binary alloy AB:
interaction energy A
A-B
B usually differs from energies A-A,
A A, B
B-B
B (real solution)
partial pressure of A in AB at T, pA partial pressure of pure A at T, pA(0)

pA=A.XA.pA(0)
A: activityy coefficient,, XA: mole fraction
Knudsen equation flux ratio

A
A X A pA (0)
MB
=
.
B B (1 - X A ) pB (0) M A
i, Mi, and T determine the vapor and film composition
SCPY663 Sem2/2009 (PhysicsMUSC)

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Is it feasible to evaporate an Al-2wt%Cu alloy at T=1350K?

Al 98 / M Al
=
Cu 2 / M Cu X Al Cu Al pCu (0) M Cu
=
15
3
pAl (0)
10
X Cu Al Cu pAl (0) M Al
=
pCu (0) 2 10 4

( Al = Cu )

the melt should have the composition 13wt-% Cu in order to compensate

for the preferential evaporation of Al
melt volume should be large to avoid composition changes
due to preferential evaporation
better: evaporation from dual sources maintained at different temperatures
If keeping
p g Al at 1350K, what should be Cu temperature
p
to have Al-2wt%Cu?
SCPY663 Sem2/2009 (PhysicsMUSC)

11

Evaporation Source
resistance-heated evaporation sources
((few V, 10-50A))
tungsten wire sources
evaporant wets W &
is retained by surface tension
refractory metal sheet sources
(Ta W
(Ta,
W, Mo)
for poor wetting evaporants or powders
crucible
cr
cible so
sources
rces
(Al2O3, BN, graphite, WC, indirectly
heated by W wires or sheets)
for evaporants that alloy
with Ta, W, Mo)
SCPY663 Sem2/2009 (PhysicsMUSC)

12

Knudsen Cell

Heater Crucible

SCPY663 Sem2/2009 (PhysicsMUSC)

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disadvantages:
contamination, alloy formation, chemical
reaction of source material and evaporant
possible outgassing of hot source material

small evaporation rates, low input power

small evaporant volume
SCPY663 Sem2/2009 (PhysicsMUSC)

14

Electron Beam Evaporator

suitable for almost all evaporants
heated filament: thermionic electron emission
no direct lines of sight filament
filament-evaporant
evaporant and
filament-substrate: no contamination of the
film/coating of the filament
electron acceleration (1...10 kV)
electron deflection by magnetic field (Lorentz force)
high
g p
power ((kW):
) can evaporate
p
high
g melting
g
point materials

water cooled crucible: material only melts at

the surface, no alloying with crucible etc.
1 W/cm2 for evaporation
0.1 W/cm2 for kinetic energy of vapor atoms
10 W/cm
W/ 2 for
f radiation
di i h
heat lloss
kW/cm2 for heat conduction into the crucible
power consumption
SCPY663 Sem2/2009 (PhysicsMUSC)

15

Electron Beam Evaporator

Crucible rotation

water cooling
flanges

SCPY663 Sem2/2009 (PhysicsMUSC)

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Electron Beam Evaporator

The electron current density je leaving the hot filament is due to thermionic emission, as expressed
by Richardson's equation:

q
q

je = AT exp
kT
2

where A is Richardsons constant ((1.20106 A/m2), q is elementaryy electronic charge,

g , and is the
work function.
The e-beam
e beam evaporation source is a relatively high intensity source, as it is not necessary to raise a
furnace or other enclosure to the temperature of the evaporant. The evaporant flux can be so
dense near the evaporant surface that it is in laminar flow. The beam intensity of e-beam
evaporators has been described with a cosn() law.

J ~ (1 C ) cos n ( ) + C J cos n ( )
with the exponent n varying from 2 to at least 6, as J increases.
Crucibles are typically made of materials with a high melt point, like Al2O3, graphite, TiN, BN, etc.,
and often cooled by water.
water
SCPY663 Sem2/2009 (PhysicsMUSC)

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Laser-beam evaporation
High energy laser beam is used to evaporate the target material. It heats the
source surface only and can be operated at a high pressure.

A laser beam evaporation

p
system:
y
1 CO2 laser, 2 ZnSe window,
3 crucible, 4 target material,
5 pump, 6 gauge,
7 mass flow controller
controller, 8 mirror,
mirror
9 substrat, 10 substrate heater

SCPY663 Sem2/2009 (PhysicsMUSC)

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Pulsed Laser deposition

pulsed
l d llaser d
deposition
i i (PLD) = "flash
"fl h evaporation"
i " method.
h d
Special deposition technique for specialized thin films of unusual stoichiometries or super-lattices.
pulsed excimer laser for evaporation directed through a viewport at a target mounted in a vacuum chamber.

condensible vapor is produced after target absorbing a

powerful laser beam strikes a target and vaporizes a thin
surface region.
vaporized region of the target ~ several hundred to 1000
angstroms thick.
conical plume of evaporant caused by ablation of the
material is created.
The axis of the vapor plume normal to the target's
target s surface;
follows a cosine distribution rule. Such a visible plume
appears when the emitted vapor is ionized by the laser,
forming a plasma.
characteristic speed of the evaporant particles (which can
be both neutrals and ions) - 3105 cm/sec ~ kinetic energy
of - 3 eV.
The
The film growth rates can approach 0.5
0 5 m/min.
m/min
KrF excimer laser most frequently used lasers
operating at wavelength=248 nm. Thus the energy carried
by
y a photon
p
is h=hc/, which should be over the energy
gy
required for an atom escaping from the solid target,
h >Econdense.
SCPY663 Sem2/2009 (PhysicsMUSC)

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Excimer laser used for PLD:

Lasermedium

ArF

KrF

XeCl

XeF

Wavelength (nm)

193

248

308

351

gy
Pulseenergy(mJ)

400

600

400

320

Averagepower (W)

10

16

11

p
)
Gaslifetime ((106pulse)

0.4
4

10

Some representative laser parameters are as follows:

i) The wave length is in the UV range
ii) A pulse on the order of 25 ns in duration (the
pulse duration,, t))
p
iii) At a power density j of 2.4108 W/cm2 at the target
The illuminating an area of the target (A) of typically 0.1 cm2
At a repetition rate (f) of 50 Hz.
The fluence of this typical pulse (j t) is thus 6 J/cm2. The incident energy per pulse is
7 W, and the average power is 30W.
SCPY663
20
300-600 mJ. The instantaneous
powerSem2/2009
is 2.410(PhysicsMUSC)

The fluence of this typical pulse (jt) is thus 6 J/cm2. The incident energy per pulse is 300600 mJ. The instantaneous power is 2.4107 W, and the average power is 30 W.
One of the most successful PLD applications has been the preparation of high temperature
superconducting thin films. PLD seems unusually effective in recreating in the thin film the
stoichiometric composition of the complex
complex, multi-component target materials; the
vaporization is so fast that segregation is nearly impossible. Sometimes preserving
stoichiometry is assisted by performing PLD with a high partial pressure (in the mtorr
range) of reactive gas, such as oxygen, due to the absence of hot filaments or other hot
components.
The drawbacks of PLD are the relatively small deposition area, poor thickness uniformity,
and the surface outgrowths that lead to a rough film surface.

SCPY663 Sem2/2009 (PhysicsMUSC)

21

Example I
Determine the rate of loss of MgO by evaporation when exposed to a temperature
of 2000K. MgO(s)=Mg(g)+O(g)
g ( ) g(g) (g) Given the Gibbs Free Energy
gy

G 0 = 1008229.6 282.2038T

SCPY663 Sem2/2009 (PhysicsMUSC)

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Sources for Evaporating multi-component film

Figure
g
12.10 Methods for evaporating
p
g multicompoment
p
films include ((a))
single source evaporation, (b) multisource simultaneous evaporation,
and (c) multisource sequential evaporation
SCPY663 Sem2/2009 (PhysicsMUSC)

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Example II
Consider a drop of water inside the room temperature vacuum chamber. If the drop
forms a hemisphere of radius r0, and if the drop remains at room temperature,
calculate the time it will take to evaporate the drop. Assume r0 = 1 mm.

SCPY663 Sem2/2009 (PhysicsMUSC)

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Evaporation rate
Gas impingement rate for thermal evaporation (Knudsen equation, Ch.2 p.8)

N ( p ph )
e = A e
2MRT

pe: equlibrium vapor pressure of the source

ph: hydeostatic pressure acting on the evaporant

Usually: ph = 0 (vacuum)

pe
pe
gK
gK
molecules
ML
22 torr
7 torr
= 3.5 10

3
.
5

10

cm 2 s
s
MT
MT

e = 5.8 10 2

M
K p
g

2
T
g torr cm s

1 ML 3

e: mass evaporation rate

typically 10-4 g/(cm2s)at 10-2 torr

!! pe = pe(T) !!
SCPY663 Sem2/2009 (PhysicsMUSC)

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Example III
An evaporator is used to deposit aluminum. The aluminum boat is maintained at a
uniform temperature of 1100 C. If the evaporator planetaryy has a radius of 40 cm
and the diameter of the crucible is 5 cm, what is the deposition rate of aluminum? If
the chamber also has a background pressure of 10-6 torr of water vapor and the
water vapor is assumed to be at room temperature, determine the ratio of the
arrival rated of the aluminum atoms and the water molecules, the mass density of
solid aluminum is 2.7 g/cm3.

SCPY663 Sem2/2009 (PhysicsMUSC)

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Planetary

SCPY663 Sem2/2009 (Physicshttp://www.edmundoptics.com/TechSupport/DisplayArticle.cfm?articleid=298

MUSC)
http://www.ifp.tuwien.ac.at/forschung/duenne_schichten/english/equipment.htm

27

Vapor pressure of selected elements

Al

1373K=1100C

SCPY663
melting
temperature Tm
Sem2/2009 (PhysicsMUSC)

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SCPY663 Sem2/2009 (PhysicsMUSC)

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Step Coverage

Aspect Ratio (AR) = step height/step diameter

Standard evaporation :
Discontinuous film for 1< AR
Marginal
for 0.5< AR<1
Continuous
for
AR <0.5
Improvements :
i) Substrate Heating
high
hi h d
deposition
iti rate
t
ii) Substrate Rotating

SCPY663 Sem2/2009 (PhysicsMUSC)

30

Angular distribution of evaporants: cosine law

Emitting flux from any point on the surface; Jv
Total evaporation rate from a source of area A; Q = JvA
dAr
r

KQ
Q
r2
cosine flux distribution J = J 0 cos
F sphere
For
h off radius
di r; J 0 =

Receiving Flux on dAr ; J =

dAs

J 0 cos cos
dAr
2
r

K = geometry factor
=

K cell
K-cell

=
Jo

Jocos

1
4
1

; point source
; disc shape source e.g. boat

Deposition rate is determined in J=J cos2

In the typical case of disc-shaped source = ;
J = Jocos4 /r2
SCPY663 Sem2/2009 (PhysicsMUSC)

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Deposition Geometry

Figure 12.3 The geometry of

deposition for a wafer
((A)) in an arbitrary
y position
p
and
(B) on the surface of a sphere.

Figure 3-4 Evaporation from (a) point source, (b) surface source.

SCPY663 Sem2/2009 (PhysicsMUSC)

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Cosn distribution

Figure 3-5 Calculated lobe-shaped vapor clouds with various cosine exponents. (From Ref.9.)
SCPY663 Sem2/2009 (PhysicsMUSC)

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Electron Beam Evaporator

The electron current density je leaving the hot filament is due to thermionic emission, as expressed
by Richardson's equation:

q
q

je = AT exp
kT
2

where A is Richardsons constant ((1.20106 A/m2), q is elementaryy electronic charge,

g , and is the
work function.
The e-beam
e beam evaporation source is a relatively high intensity source, as it is not necessary to raise a
furnace or other enclosure to the temperature of the evaporant. The evaporant flux can be so
dense near the evaporant surface that it is in laminar flow. The beam intensity of e-beam
evaporators has been described with a cosn() law.

J ~ (1 C ) cos n ( ) + C J cos n ( )
with the exponent n varying from 2 to at least 6, as J increases.
Crucibles are typically made of materials with a high melt point, like Al2O3, graphite, TiN, BN, etc.,
and often cooled by water.
water
SCPY663 Sem2/2009 (PhysicsMUSC)

34

Thickness uniformity
for point source

d0 =
; = material bulk density
4h 2
d
1
=
;
d 0 {1 + (l / h) 2 }3 / 2
for surface source

d0 =
; = material bulk density
h 2
d
1
=
d 0 {1 + (l / h) 2 }2

SCPY663 Sem2/2009 (PhysicsMUSC)

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