5482

Lecture 12:
PVD and CVD

(Physical Vapor Deposition and Chemical Vapor Deposition)
Dong-Il
g “Dan” Cho
School of Electrical Engineering and Computer Science, Seoul

National University
Nano/Micro Systems & Controls Laboratory
Thin Film Deposition (1)
• Deposition
– The transformation of vapors into solids, frequently used to grow
solid
lid thin
thi film
fil and
d powder
d materials
t i l
Physical methods Chemical methods

- Evaporation - Chemical vapor deposition
- Sputtering - Low pressure CVD
- Plasma enhanced CVD
film
Substrate
Applications:
Metalization (Al
(Al, W
W, silicide)
Poly-Si
Dielectric layers: surface passivation
Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

This material is intended for students in 4541.844 class in the Spring of 2009. Any other
usage and possession is in violation of copyright laws 2
Thin Film Deposition (2)
• Physical Vapor Deposition (PVD)
– Direct impingement of particles on the hot substrate surface
– Thermal evaporation, electron-beam evaporation, sputtering
• Chemical Vapor
p Deposition
p (CVD)
( )
– Convective heat and mass transfer as well as diffusion with
chemical reactions at the substrate surfaces
– More complex
p process
p than PVD
– More effective in terms of the rate of growth and the quality of
deposition
– LP/AP CVD, Thermal/PE/Ph/LC CVD

PVD : Evaporation (1)
Substrate - Thermal evaporator

- Materials:
M i l Au,
A Al
Al, Ti
Ti, C
Cu, Ni
Ni, C
Cr, A
Ag,
Co, Sn, Pd
Deposited
p film
Evaporated metal
Resistance
heater
Thermal Evaporation
Gas Pressure : 10-5 Torr
PVD : Evaporation (2)
Substrate - E-gun evaporator

- M
Materials:
i l Ti,
Ti C
Cr, A
Au, Al
Al, Ni,
Ni AAg
- Within wafer uniformity: < 5%
Deposited
p film - Crucible liner 6pocket crucible
Evaporated metal
Electron source
Electron Beam Evaporation
Gas Pressure : 10-5 Torr
PVD : Sputtering (1)
Cathode
- Metal sputter
- Materials: Cr, Mo, Ti, Cu , Al , W, Ni,
Pt
Target
Ar plasma
Deposited film
Substrate
Anode
Gas Pressure : 1
1~ 10 mTorr
PVD : Sputtering (2)
- Au
A sputter
tt
- Materials: Au, Ti (adhesion, Cr
(adhesion)
- Wavics sputter
- Within wafer uniformity: < 5%
- Materials: Ti, Al , Mo, Cu
- Wafer heating : 20℃ ~ 250℃

Thermal evaporation VS Sputtering
Thermal Evaporation Sputtering
Thousand atomic layers
y
Rate On atomic layer at a time
at a time
Choice of materials Limited Almost unlimited
Surface damage Very low Ionic bombardment damage
Adhesion Poor Good (on most materials)
Uniformity
y Difficult to control Easy
y to control
Can be controlled by
Film properties Difficult to control
pressure and temperature
Step coverage
Substrate Substrate

Step coverage problem with PVD (1)
• Geometrical shadowing
Flux
Film
step
p Film
Substrate

Step coverage problem with PVD (2)
• Self-shadowing
Flux
T=t
Film
T=0
step
p Film
T=0 T=t
Substrate

Methods for minimizing step coverage problems
1. Rotate +Tilt substrate during

g deposition
p
2. Elevate substrate temperature (enhance surface diffusion)
3. Use large-area deposition source

Chemical Vapor Deposition (1)
• What is Chemical Vapor Deposition?
– Chemical reactions which transform g gaseous molecules, called
precursor, into a solid material, in the form of thin film or
powder, on the surface of a substrate

Chemical Vapor Deposition (2)
Source
Ch
Chemical
i l reaction
ti
film
Substrate
More conformal deposition vs. PVD

t
t Film
step step
Substrate
CVD Reactor Parameters
Parameters Variations
Temperature range Low, Medium, High
Deposition pressure ATM, Low
Reactor geometry / Wall temp.

temp Hot wall,
wall Cold wall
Energy source Temp., R.F, UV-light
Deposition film Dielectric, Metal
Reactant / Carrier gases Metal Organic, Inorganic

Examples : CVD reactors (1)
Vertical CVD Reactor Horizontal CVD Reactor

Examples : CVD reactors (2)
D
Dome
Shower head
injector
Heater
Heater
Nozzle
injector
Vaporizer
Shower Head Injector

CVD systems
T
Type Ad
Advantage Di d
Disadvantage U
Usage P
Pressure/temp
/
APCVD
Poor step Low temp 10 ~ 100 kPa
Atmospheric Simple, fast
coverage oxides 350 ~ 1200 ˚C
C
pressure CVD
Excellent
LPCVD
cleanness, High temp, low Polysilicon, 100 Pa
Low p
pressure
conformity and deposition rate nitride oxide
nitride, 550 ~ 600 ˚C
C
CVD
uniformity
Low temp
PECVD Risc for particle
oxides
oxides, 200 ~ 600 Pa
Plasma Low temp and chemical
passivation 300 ~ 400 ˚C
enhanced CVD contamination
nitrides
APCVD is mass transport controlled, LPCVD is surface reaction controlled

Atmospheric Pressure CVD
• APCVD (Atmospheric Pressure Chemical Vapor Deposition)
– High deposition rate, poor uniformity, high contamination level,
250-450 ℃
– Cold wall process
– Material: epitaxial Si, poly
poly-Si,
Si, Si3N4, SiO2, etc.

Low Pressure CVD
• LPCVD (Low Pressure Chemical Vapor Deposition)
– Low deposition
p rate, high
g uniformity,
y 575-650 ℃
– Good uniformity, property
– Material: Si3N4, SiO2, poly-Si, etc.

LPCVD at ISRC (2)
Process name POLY Si
Dep Temp.
Dep. Temp 622℃ / 624℃ / 625℃ Dep rate
Dep. 100Å/min
Gas SiH4 : 60sccm
Process pressure 270mTorr
Process name α -Si
Dep Temp.
Dep. Temp 549 5℃ / 555℃ / 555℃
549.5℃ Dep rate
Dep. 24Å/min
Gas SiH4 : 60 sccm
Process pressure 250 mTorr
Process name Low stress Nitride
Dep Temp.
Dep. Temp 825℃ / 828℃ / 825℃ Dep rate
Dep. 27Å/min
Gas DCS-L: 21sccm, DCS-R: 30sccm,NH3-L:3.5sccm,NH3-L:5sccm
Process pressure 150mTorr

Plasma Enhanced CVD (1)
• PECVD (Plasma Enhanced Chemical Vapor Deposition)
– Ionized chemical species
p allows a lower process
p temperature.
p
– Film properties can be tailored by controllable ion bombardment
with substrate bias voltage.
– Material: Si3N4, SiO2, amorphous
amorphous-Si
Si, etc
etc.
– Faster rate and lower deposition temperature than thermal CVD
– Cracks, pin holes, and poor stoichiometry

Plasma Enhanced CVD at ISRC (2)
• P-5000 II
RF power Pressure Gas flow Dep. R ate

(W) (Torr) TEOS O2 (Å/min)
350 9 220 220 About 100

Plasma Enhanced CVD at ISRC (3)
• STS PECVD
Nitride
Gas flow (sccm) Pressure Dep. rate
RF power (W)
5%SiH4/N2 NH3 N2 (mTorr) (Å/min)
Low Frequency (187kHz),

800 10 1200 580 160
60W
Oxide
RF power (W)

160 1500 240 550 340
60W
Oxinitride
RF power (W)

800 250 60 580 300
60W
Low stress nitride

RF power (W)
5%SiH4//N2 NH3 N2 (mTorr) (Å/min)
High Frequency (13.56MHz)

Dong-il “Dan” Cho : 20W(6sec), Nano/Micro Systems & Controls Lab.
800 10 1200
This material is580
intendedLow
forFrequency
students(187kHz) 100 in the Spring of 2009. Any other
in 4541.844 class
usage and possession is in violation of copyright laws
: 20W(1.5sec) 23
Common CVD films
Thin
Typical Reactions Equipment Comments
film
200 ~ 800 ˚C
C
SiH4 + O2 Æ SiO2 +
LPCVD, 200 ~ 500 ˚C (LTO) – may require high
H2
SiO2 PECVD, T anneal.
Si(OC2H5)4(+O3) Æ
HDPCVD 25 ~ 400 ˚C ((TEOS-ozone,, PECVD,,
SiO2 + byproducts
b p od cts
HDPCVD)
3SiH4 + 4NH3 Æ
Si3N4 + 12H2 LPCVD, 650 ~ 800 ˚C for oxidation mask
Si3N4
3SiH2Cl2 + 4NH3 Æ PECVD 200 ~ 400 ˚C (PECVD) for passivation
Si3N4 + 6N2 + 6HCl
575 to 800 ˚C
Poly
Poly-
Same as epitaxial Si LPCVD Grain structure depends on deposition
silicon
conditions and doping
SiH4 Æ Si + 2H2
1000 ~ 1250 ˚CC
Epitaxial
E it i l SiCl4 + 2H2 Æ Si + APCVD,
APCVD
If using reduced pressure, 700 to 900
silicon 4HCl LPCVD
˚C
Also SiHCl3, SiH2Cl2

CVD Chemistries (1)
• Silicon Oxide
– Dryy oxidation : Si + O2 Æ SiO2
– Wet Oxidation : Si + 2H2O Æ SiO2 + 2H2
– SiH4 + O2 Æ SiO2 + 2H2
– SiH4 + N2O Æ SiO2 + byproducts
– SiCl2H2 + N2O Æ SiO2 + byproducts
– Si(OC2H5)4 Æ SiO2 + byproducts

Example : Silicon dioxide
• Thermally driven reaction
– Mid-temperature
p : ~ 500 ˚C
• “LTO” (low-temp. oxide) T < ~ 500 ˚C
– SiH4 + O2 Æ SiO2 + H2
– Cold
Cold-wall
wall, atmospheric
atmospheric, ~ 0.1
0 1 μm/min
– Hot-wall, LPCVD, ~ 0.01 μm/min
• Plasma-enhanced reaction (PECVD)
– Low temperature : ~ 250 ˚C
• High temperature: ~ 700 ˚C
– Tetraethyl orthosilicate (TEOS)
• Si(OC2H5)4 Æ SiO2 + byproducts

CVD Chemistries (2)
• Silicon Nitride
– 3SiH4 + 4NH3 Æ Si3N4 + 12H2
– 3SiH2Cl2 + 4NH3 Æ Si3N4 + byproducts
– 3SiH4 + 4N2O Æ Si3N4 + byproducts
– 3SiH4 + N2 Æ Si3N4 + byproducts

Example : Silicon nitride
• Uses
– Diffusivityy of O2, H2 is veryy low in nitride
• Mask against oxidation, protect against water/corrosion
– Diffusivity of Na also very low
• Protect against mobile ion contamination
• Deposition
– Stoichiometric formulation is Si3N4
• In practice
i Si/N
i ratio
i varies
i ffrom 0.7 (N rich)
i h to 1.1 (Sii rrich)
i h
– LPCVD : ~ 700 ˚C ~ 900 ˚C
• 3SiH4 + 4NH3 Æ Si3N4 + 12H2 ; 3SiH2Cl2 + 4NH3 Æ Si3N4 + 6N2 +
6HCl
• ρ : ~ 3 g/cm3
• Stress : ~ 10 Gdyne/cm2, tensile
– PECVD
• aSiH4 + bNH3 Æ SixNyHz+ cH2 ; aSiH4 + bN2 Æ SixNyHz+ cH2
• ρ : 2.4 ~ 2.8 g/cm3
• Stress : ~2C ~5T Gdyne/cm
d 2

CVD Chemistries (3)
• Poly-silicon : SiH4 Æ Si + 2H2
• Silicon Carbide
• Polycrystalline Diamond
• Parylene (polymerized p-xylylene)

p xylylene)
• Refractoryy Metals : 2WF6 + 3SiH4 Æ 2W + 3SiF4 + 6H2
• II-VI compounds

Exaple : polysilicon
• Uses
– Gates, high
g value resistors, “local” interconnects
• Deposition
– Silane pyrolysis : 600 ~ 700 ˚C , SiH4 Æ Si + 2H2
• Atmospheric,
Atmospheric cold wall,
wall 5% silane in hydrogen
hydrogen, ~1/2
1/2 μm/min
• LPCVD (~ 1 Torr), hot wall, 20 ~ 100% silane, ~ hundreds nm/min
– Grain size dependent on growth temperature, subsequent
processing
i
• 950 ˚C phosphorus diffusion, 20 min; ~ 1 μm grain size
• 1050 ˚C oxidation; 1~3 μm grain size
• In-situ doping
– P-type: diborane B2H6
• Can cause substantial increase in deposition
p rate
– N-type: arsine AsH3, phosphine PH3
• Can cause substantial decrease in deposition rate
• Dope after deposition (implant,
(implant diffusion)
CVD mechanisms

Example Poly-Si deposition
(1) gas-phase decomposition and (2) transport to the surface of the

wafer. At the surface the growth species must (3) adsorb, (4) diffuse,
and ((5)) decompose,
p , and (6)
( ) the reaction byproducts
yp are desorbed.
Kinetics of CVD thin film deposition (1)
• We consider the fluxes for the two
important process such as mass Boundary
transfer and surface reaction.
reaction l
layer
• F1 = diffusion flux of reactant species
Gas Silicon
to the wafer = mass transfer flux.
F1 = hG(CG-CC S) CG
• Where (CG-CS) term is the difference in
concentration of the reactants species
between the main g gas flow and the
wafer surface, and hG is the mass F1
transfer coefficient.
Cs
• Similarly, F2 = flux of reactant
consumed dbby the
th surface
f reaction
ti =
surface reaction flux.
F2 = KSCS F2
• Where KS is the chemical surface
reaction rate and CS is the
concentration of the reacting species at
the surface.
This material is intended for students in 4541.844 class in the Spring of 2009. Any other 33
• In steady state
hG
F1 = F2 Æ CS = CG
(h G + k S )
Growth Rate
RG = F2/NSi (NSi : # of Si atoms in a unit volume)
1 hGk S
RG = CG
NSi hG + k S
Surface reaction rate
EA
k S = k 0exp(− )
kT
EA : activation energy
k : Boltzmann constant
This material is intended for students in 4541.844 class in the Spring of 2009. Any other 34
• Limiting cases of growth rate
1. If KS << hG, then we have the surface reaction controlled case:
1
RG = k SCG
NSi
2. If hG << KS, then we have the mass transfer, or gas phase
diffusion controlled case:
1
RG = hGCG
NSi

Deposition rate versus Temp
high T Å Æ low T
• KS limited deposition is VERY temp sensitive
sensitive.
• hG limited deposition is VERY geometry sensitive.
• Si epi deposition often done at high T to get high quality single crystal
growth.
∴ hG controlled.
• Polysilicon is usually deposited at lower temperature surface reaction regime.
regime
Step Coverage Profile (1)
• Step coverage profile
A: Rapid surface migration process (before reaction), yielding uniform coverage since
reactants adsorb and move, then react
B: Long mean free path process and no surface migration, with reactant molecule
arrival angle determined location on features (local “field
field of view”
view effects are
important)
C: Short mean free path process with no surface migration, yielding nonconformal
coating

• Key Parameters
– Mean Free Path
– Surface Migration Energy ( E ∝ Temperature)
– Arrival angle
• For conformal step coverage

– α < l ((mean free path)
p )
– α = arctan (w/z)
– High Surface Mobility
• Process tendency
– A: LPCVD
– B: PECVD
Evaporated & Sputtered Metal

• Step coverage profile example
Good Bad

Impact of pressure on deposition conditions (1)
• Material arrival angular distribution
– Depends
p on mean free path
p compared
p to both size of system
y
and size of wafer “steps”
• Case I: “atmospheric pressure”: 760 Torr Æ λ = 0.07 μm
– Isotropic arrival on ALL surfaces
Assume material does not migrate after arrival.

• Case II: 10-1 Torr Æ λ = 0.5 mm
– Small compared
p to system,
y large
g compared
p to wafer features
– Isotropic arrival at “flat” surface
• But no scattering inside “hole”
– Shadowing
Sh d i by
b corners off features
f t
– “anisotropic” deposition

• Case II: 10-5 Torr Æ λ = 5 m
– Long
g compared
p to almost everything
y g
• Anisotropic arrival at all surfaces
– Very thin on “side walls”
– Very
V d
dependent
d t on source configuration
fi ti relative
l ti tto sample
l
surface

Dielectric deposition applications summary

Common CVD deposition reactants

CVD Hazards
• Many gases used in CVD systems are toxic (hazardous to humans), corrosive
(causes corrosion to stainless steel and other metals), flammable (burns when
exposed to an ignition source and an oxygen source)
source), explosive and/or
pyrophoric (spontaneously burn or explode in air, moisture or when exposed
to oxygen)

Reference
• R. C. Jaeger, “Introduction to Microelectronic Fabrication,” 2nd edition
• http://www.dowcorning.co.jp
• M Madou
M. Madou, “Fundamentals
Fundamentals of Microfabrication,
Microfabrication ” 2nd edition
• C. Liu, “Foundations of MEMS,” 1st edition
• J.M. Bustillo, R. T. Howe, and R. S. Muller, “Surface micromachining
for microelectromechanical systems ,,“ Proceedings of the IEEE, Vol.
86, No. 8, pp. 1552-1574, 1998
• Marc J. Madou, “Fundamentals of MICROFABICATION,” 2nd edition
• S. Lee, C. Cho, J. Kim, S. Park, S. Yi, J. Kim, and D. Cho, “The Effects
off P
Post-deposition
t d iti Processes
P on Polysilicon
P l ili Young's
Y ' M
Modulus,”
d l ” IOP JJ.
of Micromechanics and Microengineering, Vol. 8, No. 4, pp. 330-337,
1998
• S. Lee,, C. Cho,, J. Kim,, S. Park,, S. Yi,, J. Kim,, and D. Cho,, “Mechanical
Properties of Phosphorus-doped Polysilicon Films”, Journal of the
Korean Physical Society, Vol. 33, pp. 392-395, 1998
• S. Lee, and D. Cho. “The Effects of Texture on the Young’s Modulus
of Polysilicon”
Polysilicon , 1998 MRS Spring Meeting,
Meeting 1998 1998.

Reference
• K. Lee, and Y Kim, "Uniformity Improvement of Micromirror Array for
Reliable Working Performance as an Optical Modulator in the
Maskless Photolithography g p y System,”
y , Journal of Semiconductor
Technology and Science, Vol. 1, No. 2, 2001
• G. Li, and A. A. Tseng, “Low stress packaging of a micromachined
accelerometer,” Electronics Packaging Manufacturing, IEEE
Transactions on on, Vol
Vol. 24
24, No
No. 11, pp
pp. 18-25
18-25, 2001
• P. Melvas, E. Kalvesten, and G. Stemme, “A surface-micromachined
resonant-beam pressure-sensing structure,” Microelectromechanical
Systems, Journal of , Vol. 10, No. 4, pp. 498-502, 2001
• K. Meng-Hsiung, O. Solgaard, R. S. Muller, and K. Lau, ”Silicon-
micromachined micromirrors with integrated high-precision actuators
for external-cavity semiconductor lasers,” Photonics Technology
Letters,, IEEE,, Vol. 8,, No. 1,, pp.
pp 95-97,, 1996
• P. J. French and P. M. Sarro, “Surface versus bulk micromachining:the
contest for suitable applications”, IOP J. of Micromechanics and
Microengineering, Vol. 8, pp. 45-53, 1998
• G
Gregory T.
T A.
A Kovacs,
K “Micromachined
“Mi hi d Trensducers
T d Sourcebook,”
S b k ” 1st
1 t
edition
• J. D. Lee, “Silicon Integrated Circuit microfabrication technology,”
2nd edition
Reference
• http://chiuserv.ac.nctu.edu.tw/~htchiu/cvd/home.html
• http://www.plasmas.org
p // p g
• Brian Chapman, "Glow Discharge Processes: Sputtering and
Plasma Etching", John Wiley & Sons, 1980.
• Lieberman,
Li b "P
"Principles
i i l off plasma
l di
discharges
h and
d materials
t i l
processing" John Wiley & Sons, 1994


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Lecture 12:

PVD and CVD

School of Electrical Engineering and Computer Science, Seoul

Physical methods Chemical methods

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Substrate - Thermal evaporator

Substrate - E-gun evaporator

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

1. Rotate +Tilt substrate during

2. Elevate substrate temperature (enhance surface diffusion)

3. Use large-area deposition source

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

More conformal deposition vs. PVD

Temperature range Low, Medium, High

Deposition pressure ATM, Low

Reactor geometry / Wall temp.

Energy source Temp., R.F, UV-light

Deposition film Dielectric, Metal

Reactant / Carrier gases Metal Organic, Inorganic

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Vertical CVD Reactor Horizontal CVD Reactor

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

APCVD is mass transport controlled, LPCVD is surface reaction controlled

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Gas SiH4 : 60sccm

Process pressure 270mTorr

Process name α -Si

Gas SiH4 : 60 sccm

Process pressure 250 mTorr

Process name Low stress Nitride

Gas DCS-L: 21sccm, DCS-R: 30sccm,NH3-L:3.5sccm,NH3-L:5sccm

Process pressure 150mTorr

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

RF power Pressure Gas flow Dep. R ate

350 9 220 220 About 100

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Low Frequency (187kHz),

Low Frequency (187kHz),

Low Frequency (187kHz),

Low stress nitride

High Frequency (13.56MHz)

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

– Wet Oxidation : Si + 2H2O Æ SiO2 + 2H2

– SiH4 + O2 Æ SiO2 + 2H2

– SiH4 + N2O Æ SiO2 + byproducts

– SiCl2H2 + N2O Æ SiO2 + byproducts

– Si(OC2H5)4 Æ SiO2 + byproducts

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

– 3SiH2Cl2 + 4NH3 Æ Si3N4 + byproducts

– 3SiH4 + 4N2O Æ Si3N4 + byproducts

– 3SiH4 + N2 Æ Si3N4 + byproducts

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

Dong-il “Dan” Cho Nano/Micro Systems & Controls Lab.

• Parylene (polymerized p-xylylene)