II.

Thin Film Deposition

Physical Vapor Deposition (PVD)
- Film is formed by atoms directly transported from source to the substrate
through gas phase
• Evaporation
• Thermal evaporation «
• E-beam evaporation «
• Sputtering
• DC sputtering «
• DC Magnetron sputtering «
• RF sputtering «
• Reactive PVD

Chemical Vapor Deposition (CVD)

- Film is formed by chemical reaction on the surface of substrate
• Low-Pressure CVD (LPCVD) «
• Plasma-Enhanced CVD (PECVD) «
• Atmosphere-Pressure CVD (APCVD)
• Metal-Organic CVD (MOCVD)

Oxidation
Spin Coating
Platting

Applied Physics 298r 1 E. Chen (4-12-2004)

General Characteristics of Thin Film Deposition
• Deposition Rate
• Film Uniformity
• Across wafer uniformity
• Run-to-run uniformity
• Materials that can be deposited
• Metal
• Dielectric
• Polymer
• Quality of Film – Physical and Chemical Properties
• Stress
• Adhesion
• Stoichiometry
• Film density, pinhole density
• Grain size, boundary property, and orientation
• Breakdown voltage
• Impurity level
• Deposition Directionality
• Directional: good for lift-off, trench filling
• Non-directional: good for step coverage
• Cost of ownership and operation

Applied Physics 298r 2 E. Chen (4-12-2004)

 Evaporation

¨ Load the source material-to-be-

deposited (evaporant) into the
container (crucible) Substrate
Film

¨ Heat the source to high

temperature
¨ Source material evaporates Evaporant
Vapor
¨ Evaporant vapor transports to and
Impinges on the surface of the
Current
substrate Crucible (energy source)
¨ Evaporant condenses on and is
adsorbed by the surface

Applied Physics 298r 3 E. Chen (4-12-2004)

 Langmuire-Knudsen Relation
Mass Deposition Rate per unit area of source surface: Substrate

1
M  1
Rm = Cm   cos θ cos ϕ 2 (Pe (T ) − P )
2
r
T  r
θ
ϕ
Cm = 1.85x10-2
r: source-substrate distance (cm) P
T: source temperature (K)
Pe: evaporant vapor pressure (torr), function of T
P: chamber pressure (torr) Pe
M: evaporant gram-molecular mass (g)

¬ Maximum deposition rate reaches at high Source (K-Cell)

chamber vacuum (P ~ 0)

Applied Physics 298r 4 E. Chen (4-12-2004)

 Uniform Coating
Spherical surface with source on its edge: Spherical Surface

r
cos θ = cos ϕ =
2r0 ϕ
1 r
 M  Pe 2 r0 θ
Rm = Cm   2
 T  4r0 P

Pe
¨ Angle Independent – uniform coating!

Source (K-Cell)
¬ Used to coat instruments with spherical surfaces

Applied Physics 298r 5 E. Chen (4-12-2004)

 Uniformity on a Flat Surface
Consider the deposition rate difference
between wafer center and edge:
W /2
1 Wafer
R1 ∝ 2
r1

1 r
2
ϕ
R2 ∝ 2 cos 2 θ = 1 4 r1
r2 r2 θ r2
Define Uniformity:
P
R1 − R2
σ (% ) = (% )
R1 Pe
−2
  W 2  W 2
W
σ = 1 − 1 +    ≈ 2 or = 2σ Source (K-Cell)
  2r1   2r1 r1
 

Applied Physics 298r 6 E. Chen (4-12-2004)

 Uniformity Requirement on a Flat Surface
Source-substrate distance requirement:
160
W
r>

Source-Sample Distance (r)

140
2σ 1%

120 2%
5%
In practice, it is typical to double this 100 10%
number to give some process margin:
80

60
2
r >W
σ
40

20

Larger r Means: 0
0 2 4 6 8 10
¬ bigger chamber
Sample Size (W)
¬ higher capacity vacuum pump
¬ lower deposition rate
Another Common Solution:
¬ higher evaporant waste off-axis rotation of the sample

Applied Physics 298r 7 E. Chen (4-12-2004)

 Thickness Deposition Rate vs. Source Vapor Pressure
dh Rm Substrate
Thickness deposition rate = Ae
dt ρ Film
1 dh
dh Ae M  1
= Cm   cos θ cos ϕ 2 Pe (T )
2
r
dt ρ T  r
θ
T: source temperature (K) ϕ
Ae: source surface area (cm2)
ρ: evaporant density (g/cm3) Ae
P
Pe is function of source Temperature!
Pe
Example: Al T
M ~ 27, ρ ~ 2.7, Ae ~ 10-2 cm2, T ~ 900 K
R ~ 50 cm (uniformity requirement)
Source (K-Cell)
dh
= 50 Pe (A/s) ¬ The higher the vapor pressure, the higher the material’s
dt deposition rate

Applied Physics 298r 8 E. Chen (4-12-2004)

 Deposition Rate vs. Source Temperature
Typically for different material:

dh
= (10 ~ 100) Pe (T ) ( A / s)
dt

• For deposition rate > 1 A/s:

Pe > ~ 100 mtorr
• Pe depends on: 1) materila
and 2) temperature
• Deposition rates are
significantly different for
different materials
• Hard to deposit multi-
Example: for Pe > 100 mtoor
component (alloy) film
T(Al) > 1400K, T(Ta) > 2500K
without losing stoichiometry

Applied Physics 298r 9 E. Chen (4-12-2004)

 Heating Method – Thermal (Resist Heater)

Source
Material
Resistive
Current
Wire Foil Dimple Boat

Crucible
Alumina Coated
Foil Dimple Boat
Contamination Problem
with Thermal Evaporation
Container material also evaporates, which
contaminates the deposited film
Cr Coated Tungsten Rod

Applied Physics 298r 10 E. Chen (4-12-2004)

 CIMS’ Sharon Thermal Evaporator

Applied Physics 298r 11 E. Chen (4-12-2004)

 Heating Method – e-Beam Heater

e-
Electron Beam

Crucible Magnetic Field

Focusing
Aperture
Evaporant Evaporant (beam focusing
& positioning)

Cathode Filament

Water Cooled Rotary Copper Hearth Advantage of E-Beam Evaporation:

(Sequential Deposition)
Very low container contamination

Applied Physics 298r 12 E. Chen (4-12-2004)

 CIMS’ Sharon E-Beam Evaporator

Applied Physics 298r 13 E. Chen (4-12-2004)

 Comparison

Typical Deposition Temperature

Deposition Material Impurity Cost
Evaporant Rate Range

Au, Ag, Al, Cr, Sn,

Sb, Ge, In, Mg,
Metal or low Ga
Thermal melt-point High 1 ~ 20 A/s ~ 1800 ºC Low
materials CdS, PbS, CdSe,
NaCl, KCl, AgCl,
MgF2, CaF2, PbCl2

Everything above,
plus:
Both metal
Ni, Pt, Ir, Rh, Ti, 10 ~ 100
E-Beam and Low ~ 3000 ºC High
V, Zr, W, Ta, Mo A/s
dielectrics
Al2O3, SiO, SiO2,
SnO2, TiO2, ZrO2

Stoichiometrical Problem of Evaporation

• Compound material breaks down at high temperature
• Each component has different vapor pressure, therefore different deposition
rate, resulting in a film with different stoichiometry compared to the source

Applied Physics 298r 14 E. Chen (4-12-2004)

 Typical Boat/Crucible Material

Refractory Metals
Temperature for 10-mtorr
Melting Point
Material Vapor Pressure (Pe)
(ºC)
(ºC)

Tungsten (W) 3380 3230

Tantalum (Ta) 3000 3060

Molybdenum (Mo) 2620 2530

Refractory Ceramics
Graphitic Carbon (C) 3799 2600

Alumina (Al2O3) 2030 1900

Boron Nitride (BN) 2500 1600

Applied Physics 298r 15 E. Chen (4-12-2004)

 DC Diode Sputtering Deposition
• Target (source) and substrate are placed 2 – 5kV
on two parallel electrodes (diode)
• They are placed inside a chamber filled
with inert gas (Ar)
• DC voltage (~ kV) is applied to the diode Target (Cathode)
• Free electron in the chamber are e- e-

accelerated by the e-field

γ
• These energetic free electrons inelastically Ar Ar+
e- Ar

collide with Ar atoms

’ excitation of Ar ¨ gas glows Substrate (Anode)
’ ionization of Ar ¨ Ar+ + 2nd electron
• 2nd electrons repeat above process
¨ “gas breakdown”
¨ discharge glow (plasma)

Applied Physics 298r 16 E. Chen (4-12-2004)

 Self-Sustained Discharge
• Near the cathode, electrons move much faster than ions
because of smaller mass 2 – 5kV
¬ positive charge build up near the cathode, raising
the potential of plasma
¬ less electrons collide with Ar
¬ few collision with these high energetic electrons
results in mostly ionization, rather than excitation
¬ dark zone (Crookes Dark Space) Target (Cathode)
• Discharge causes voltage between the electrodes
+ + + + + Crookes
Dark Space
reduced from ~103 V to ~102V, mainly across the dark
Ar+ Ar+
space
t t
• Electrical field in other area is significantly reduced by
screening effect of the position charge in front of
cathode
• Positive ions entering the dark space are accelerated Substrate (Anode)
toward the cathode (target), bombarding (sputtering) the
target
¬ atoms locked out from the target transport to the
substrate (momentum transfer, not evaporation!)
¬ generate 2nd electrons that sustains the discharge
(plasma)

Applied Physics 298r 17 E. Chen (4-12-2004)

Requirement for Self-Sustained Discharge
• If the cathode-anode space (L) is less than the dark space length
¬ ionization, few excitation
¬ cannot sustain discharge
• On the other hand, if the Ar pressure in the chamber is too low
¬ Large electron mean-free path
¬ 2nd electrons reach anode before colliding with Ar atoms
¬ cannot sustain discharge either

Condition for Sustain Plasma: L ⋅ P > 0.5 (cm ⋅ torr )

L: electrode spacing, P: chamber pressure

For example:
Typical target-substrate spacing: L ~ 10cm
¨ P > 50 mtorr

Applied Physics 298r 18 E. Chen (4-12-2004)

 Deposition Rate vs. Chamber Pressure
High chamber pressure results in low deposition rate

Mean-free path of an atom in a gas ambient:

In fact, sputtering deposition rate R:
5 × 10 −3
λ~ (cm)
P (torr ) 1
R∝
L⋅P
Use previous example:
L = 10 cm, P = 50 mtorr
’ Large LP to sustain plasma
¨ λ ~ 0.1 cm
¨ sputtered atoms have to go through ’ small LP to maintain good
hundreds of collisions before reaching the
deposition rate and reduce
substrate
¨ significantly reduces deposition rate random scattering
¨ also causes source to deposit on chamber ?
wall and redeposit back to the target

Applied Physics 298r 19 E. Chen (4-12-2004)

 DC Magnetron Sputtering

• Using low chamber pressure to maintain high deposition rate

• Using magnetic field to confine electrons near the target to sustain plasma

E
e-
+ B +
Cathode (Target) S N S

Apply magnetic field parallel to the

cathode surface
Target
¨ electrons will hope (cycloid) near the
S N S
surface (trapped)

Applied Physics 298r 20 E. Chen (4-12-2004)

 Impact of Magnetic Field on Ions

Hoping radius r:

1 2m
r~ Vd
B e Ar+

Vd – voltage drop across dark space e-

(~ 100 V) E
B – Magnetic field (~ 100 G) r
+ B

Cathode (Target)

For electron r ~ 0.3 cm

For Ar+ ion: r ~ 81 cm

Applied Physics 298r 21 E. Chen (4-12-2004)

 As A Result …

¬ current density (proportional to ionization rate) increases by 100 times

¬ required discharge pressure drops 100 times
¬ deposition rate increases 100 times

Magnetron
Deposition Rate (R)

Non-Magnetron
~ 1mT

~ 100mT

Chamber Pressure (P)

Applied Physics 298r 22 E. Chen (4-12-2004)

 RF (Radio Frequency) Sputtering
DC sputtering cannot be used for depositing
dielectrics because insulating cathode will cause 13.56 MHz
charge build up during Ar+ bombarding ~
¨ reduce the voltage between electrodes
¨ discharge distinguishes
Target
Solution: use AC power
• at low frequency (< 100 KHz), both electrons and Target Sheath
ions can follow the switching of the voltage – e- e-
Ar
¨ DC sputtering Ar+
t

• at high frequency (> 1 MHz), heave ions cannot no Substrate Sheath

long follow the switching
¨ ions are accelerated by dark-space (sheath) Substrate
voltage
¨ electron neutralizes the positive charge buildup on
both electrodes
• However, there are two dark spaces
¨ sputter both target and substrate at different cycle

Applied Physics 298r 23 E. Chen (4-12-2004)

 RF (Radio Frequency) Sputtering
13.56 MHz
n
VT A  ~
∝  S  (n ~ 2)
VS  AT 

AT Target
VT – voltage across target sheath
VT
Vs – voltage across substrate sheath
AT – area of target electrode
As – area of substrate electrode
VS
AS
Substrate

Larger dark-space voltage develops at the

electrode with smaller area
¨ make target electrode small

Applied Physics 298r 24 E. Chen (4-12-2004)

 Comparison between Evaporation and Sputtering

Evaporation Sputtering

High energy atoms / ions

Low energy atoms
(~ 0.1 eV)
High Vacuum
• directional, good for lift-off
• lower impurity
(1 – 10 eV)
• denser film
• smaller grain size
• better adhesion
Low Vacuum
• poor directionality, better step coverage
• gas atom implanted in the film

Point Source Parallel Plate Source

• poor uniformity • better uniformity

Component Evaporate at Different Rate All Component Sputtered with Similar Rate
• poor stoichiometry • maintain stoichiometry

Applied Physics 298r 25 E. Chen (4-12-2004)

 Chemical Vapor Deposition (CVD)
Deposit film through chemical reaction and surface absorption

• Introduce reactive gases to the chamber

• Activate gases (decomposition)
A B A B
¬ heat
¬ plasma
• Gas absorption by substrate surface A B A B

• Reaction take place on substrate surface; W W

film firmed
Substrate
• Transport of volatile byproducts away
form substrate
• Exhaust waste

Applied Physics 298r 26 E. Chen (4-12-2004)

 Types of CVD Reactions
Pyrolysis (Thermal Decomposition)
AB ( gas ) → A ( solid ) + B ( gas )

Example
α-Si deposited at 580 - 650 ºC:

SiH 4 ( gas ) = Si ( solid ) + 2 H 2 ( gas )

Reduction (lower temperature than Pyrolysis)

AB ( gas ) + H 2 ( gas, commonly used ) ↔ A ( solid ) + HB ( gas )
Example
W deposited at 300 ºC:

WF6 ( gas ) + 3H 2 ( gas ) = W ( solid ) + 6 HF ( gas )

Reversible process, can be used for chamber cleaning

Applied Physics 298r 27 E. Chen (4-12-2004)

 Types of CVD Reactions (Cont.)
Oxidation

AB ( gas or solid ) + O2 ( gas, commonly used ) ↔ AO ( solid ) + [O ]B ( gas )

Example
Low-temperature SiO2 deposited at 450 ºC:

SiH 4 ( gas ) + O2 ( gas ) = SiO2 ( solid ) + 2 H 2 ( gas )

Example
SiO2 formed through dry oxidation at 900 - 1100 ºC:

Si ( Solid ) + O2 ( gas ) = SiO2 ( solid )

Applied Physics 298r 28 E. Chen (4-12-2004)

 Types of CVD Reactions (Cont.)
Compound Formation

AB ( gas or solid ) + XY ( gas or solid ) ↔ AX ( solid ) + BY ( gas )

Example
SiO2 formed through wet oxidation at 900 - 1100 ºC:

Si ( Solid ) + 2 H 2O(vapor ) = SiO2 ( solid ) + 2 H 2

Example
SiO2 formed through PECVD at 200 - 400 ºC:

Si H 4 ( gas ) + 2 N 2O( gas ) = SiO2 ( solid ) + 2 N 2 + 2 H 2

Example
Si3N4 formed through LPCVD at 700 - 800 ºC:

3Si H 2Cl2 ( gas ) + 4 NH 3 ( gas ) = Si3 N 4 ( solid ) + 6 H 2 + 6 HCl

Applied Physics 298r 29 E. Chen (4-12-2004)

 CVD Deposition Condition
Mass-Transport Limited Deposition
- At high temperature such that the reaction rate
exceeds the gas delivering rate
- Gas delivering controls film deposition rate

Deposition Rate (log)

- Film growth rate insensitive to temperature
- Film uniformity depends on whether reactant Mass-Transport
Limited
can be uniformly delivered across a wafer and Regime
wafer-to-wafer
Reaction-Rate
Limited
Reaction-Rate Limited Deposition Regime

- At low temperature or high vacuum such that

the reaction rate is below gas arriving rate 1/T (K)

- Temperature controls film deposition rate

- Film uniformity depends on temperature
uniformity across a wafer and wafer-to-wafer

Applied Physics 298r 30 E. Chen (4-12-2004)

 Low-Pressure CVD (LPCVD)

Heater Heater Heater

Reactant Exhausted
Wafer
Gas Gas
Horizontal
Quartz Tube
Z-1 Z-2 Z-3

• Thermal energy for reaction activation

• System works at vacuum (~ 0.1 – 1.0 torr), resulting in high diffusivity of reactants
¨ reaction-rate limited
• Wafer can stacked closely without lose uniformity as long as they have the same
temperature
• Temperature is controlled around 600 - 900ºC by “flat” temperature zone through using
multiple heaters
• Low gas pressure reduce gas-phase reaction which causes particle cluster that
contaminants the wafer and system

Applied Physics 298r 31 E. Chen (4-12-2004)

 Plasma-Enhanced CVD (PECVD)

RF
• Use rf-induced plasma (as in sputtering
Gases
~
case) to transfer energy into the reactant
gases, forming radicals (decomposition)
• Low temperature process (< 300 ºC)
• For depositing film on metals and other
B
Shaw Heads
materials that cannot sustain high e- e- e-
A A+ B+
temperature e-

• Surface reaction limited deposition;

substrate temperature control (typically Substrate
cooling) is important to ensure uniformity

Applied Physics 298r 32 E. Chen (4-12-2004)

 Common CVD Reactants

Material LPCVD PECVD

SiH4
α-Si SiH4
SiH2Cl2

Si(OC2H5)4 (TEOS) SiH4 + N2O

SiO2
SiH2Cl2 + N2O SiH4 + O2

SiH4 + NH3 SiH4 + NH3

Si3N4
SH2Cl2 + NH3 SiH4 + N2

Applied Physics 298r 33 E. Chen (4-12-2004)

 Comparison of Typical Thin Film Deposition Technology

Film Deposition Substrate

Process Material Uniformity Impurity Grain Size Directional Cost
Density Rate Temperature

Metal or
low
Thermal 10 ~ 100
melting- Poor High Poor 1 ~ 20 A/s 50 ~ 100 ºC Yes Very low
Evaporation nm
point
materials
Both metal
E-beam and 10 ~ 100
dielectrics Poor Low Poor 10 ~ 100 A/s 50 ~ 100 ºC Yes High
Evaporation nm

Both metal Metal:

and ~ 100 A/s Some
Sputtering dielectrics Very good Low ~ 10 nm Good ~ 200 ºC High
Dielectric: degree
~ 1-10 A/s

Mainly 10 ~ 100 Some

PECVD Good Very low Good 10 - 100 A/s 200 ~ 300 ºC Very High
Dielectrics nm degree

Mainly
LPCVD Very Good Very low 1 ~ 10 nm Excellent 10 - 100 A/s 600 ~ 1200 ºC Isotropic Very High
Dielectrics

Applied Physics 298r 34 E. Chen (4-12-2004)