6.

Thin Film Deposition Methods 1

Special Lecture on Nanofabrication, 2018 Spring, Han-Bo-Ram Lee

HBRL Research Group

Prof. Han-Bo-Ram Lee
Department of Materials Science and Engineering
Incheon National University, Korea

Thin Films in ULSI

• Many different films are used in ULSI:

conductors, insulators, and semiconductors
• Film deposition is basic ULSI process to “add”
materials

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Method Forming Thin Films
• Thermal treatment
O2
- Thermal oxidation (SiO2) diffuse-in
- Silicidation: titanium silicide (TiSi2)
• Spin on Films
Si
- Spin on Glass (SOG)
• Deposition
- Chemical Vapor Deposition (CVD) SiO2
✦ APCVD (atmospheric pressure) Si
✦ LPCVD (low pressure)
✦ PECVD (plasma enhanced)
✦ Epitaxial Growth (single-crystal films)
- Physical Vapor Deposition (PVD)
✦ Sputter
✦ Evaporation
- Electroplating
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Physical Vapor Deposition

• Deposition without chemical reaction
• Species to form films are physically “dislodged” from a source as a vapor: this
vapor is transported to substrate.

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Evaporation
• Simplest thin films deposition technique using evaporation (or sublimation) of solid
source either by thermal or e-beam evaporation
• Not the main deposition technique now for semiconductor industry (limited step
coverage, less reliability) any more, but still used for some specific purpose

Thermal evaporation E-beam evaporation

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Properties of Evaporation
• Wide utilization for Al Deposition
• A material located in a source is heated by direct resistance, electron beam,
radiation ect.
• The process is usually carried out in vacuum
• Films can be deposited at high rate (e.q. 0.5 μm/min for Al)
• Low energy of the impinging metal atoms onto the substrate ( ~ 0.1eV)

Pressure (Torr) Mean free path (cm) Collisions/sec.

10-2 0.5 9x 104
10-4 51 900
10-5 510 90
10-7 51000 0.9
10-9 5100000 9x 10-3

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Apparatus of Evaporation

• Vacuum deposition system consisting of a vacuum chamber, a mechanical

roughing pump, a diffusion pump, TMP, valves, vacuum gauges, and other
instrumentation

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Source Loading

• Many types of source loading for thermal evaporation

• Boat and filament types are popular

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 E-beam Sources

• The ingot is held at a positive potential

relative to the filament.
• A magnetic field is employed to direct the
electron beam from its source to the ingot
location.
• An additional electric field can be used to
steer the beam over the ingot surface
allowing uniform heating.

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Sputtering
• Thin film deposition by energetic ion bombardment, which physically dislodge atoms
from “target” surface
• The atom/atom clusters eject with 10 - 50 eV kinetic energy: additional surface mobility
on thin films giving better step coverage

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Sputtering vs. Evaporation
• For multicomponent thin films, sputtering yields better composition control by
compound target: Evaporation depends on vapor pressure.
• Sputtering has better lateral uniformity: sputtering target can have much larger area
than evaporating source.
• Sputtering produces better films properties: energies of incoming particles has
higher kinetic energy

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Various Sputtering Techniques

• DC diode: slow deposition, (due to high pressure to maintain

plasma > 20 - 200 mTorr), high voltage, low current, inadequate
for dielectric deposition due to charging, arcing

• RF: eliminating charging (for oxides), higher density, higher

deposition rate

• Magnetron sputtering: HDP, high deposition rate, low pressure (1

mTorr), low particle formation, reliable

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Magnetron Sputtering

• Intrinsic non-uniformity due to etch path, especially at short throw. (typically 3

- 10 cm)
• Target utilization is poor

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Properties of Sputtering
• Target size larger than sample, distance optimization
• Heart shaped magnetron to address erosion profile: Typical modern tools

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Step Coverage
• Step Coverage (conformality) is one of the most important structural properties of
thin films (usually given in %)

t
H
s
• Aspect ratio: AR =
W
H
s
• Sidewall step coverage: Cside =
b t
b
W • Bottom step coverage: Cbottom =
t

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Step Coverage of Sputtering

• Sputtering is isotropic deposition, especially short throw with large target (but better
than evaporation)
• Shadowing effect: overhang, bottom sidewall notch are problem especially for VLSI
application (eg. dual damascene), need to improve step coverage (better conformality),
especially difficult to grow at high AR structures

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Chemical Vapor Deposition (CVD)
• Chemical vapor deposition (CVD): use chemical precursor to deposit thin films through
chemical reaction

https://www.youtube.com/watch?v=j80jsWFm8Lc

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

CVD Process
• CVD process: slowest process determines overall process (rate limiting step)

wikipedia.org

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Example: Si CVD by SiH4

SiH4(g) → Si(s) + 2H2(g)

• For better uniformity, use carrier gas (H2) : gas depletion effects
• Gas phase reaction produces Si powders: particle contamination

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Chemical Reactions for CVD

1. Thermal decomposition: element films deposition
• Hydrocarbon decomposition: CH4(g) →C(s) + 2H2(g)

• Hydride decomposition: SiH (g) →Si(s) + 2H (g)

4 2
• Carbonyl decomposition: Ni(CO)4(g) →Ni(s) + 4CO(g)

• Metal organic decomposition: CH SiCl (g) →SiC(s) + 3HCl(g)

3 3
• Halide decomposition: WF6(g) →W(s) + 3F2(g)

2. Reduction/co-reduction: at lower T than thermal decomposition

• Halide reduction by hydrogen SiCl4(g) + 2H2(g) →Si(s) + 4HCl(g)

• Metal reduction of halides: TiI (g)+2Zn(s) → Ti(s) + 2ZnI (g)

4 2
• Binary compound: TiCl4(g) + 2BCl3(g) +5H2(g) →TiB2(s) + 10HCl(g)

3. Oxidation and hydrolysis

• Oxidation: SiH4(g) + O2(g)→ SiO2(s) + 2H2(g)

SiCl4(g) +2CO2(g)+2H2(g)→ SiO2(s) +4HCl+ 2CO(g)

• Hydrolysis: 2AlCl3(g) +3H2O→ Al2O3(s) + 6HCl(g)

4. Reactions to form compounds

• Carbide formation: TiCl (g) + CH (g) → TiC(s) + 4HCl(g)
4 4
• Nitride formation: 3SiH4(g) + 4NH3(g) → Si3N4(s) + 12HI2(g)

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 CVD Precursors
• Requirements for CVD precursor
- Thermal stability
- Ability to react cleanly
- Sufficient volatility
- Easy to handle

• Inorganic precursors
- Halides (chloride, fluorides…): TiCl4, WF6…
- Oxyhalides: ReOCl5…
- Hydride: SiH4, BH3…

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Classification of CVD
• Temperature provision • Pressure range
- Hot-wall CVD - APCVD (Atmospheric Pressure CVD): 1 atm
- Cold-wall CVD - LPCVD (Low Pressure CVD): mTorr ~ Torr
- *RT-CVD - UHV-CVD (GS-MBE, CBE)

• Shape of the reactor • Precursor

- Horizontal type - MO CVD
- Vertical type - Hydride CVD
- Pancake type
• # of wafers
- Barrel type
-Batch type
• Energy source -Single wafer
- Thermal CVD
- PE-CVD (Plasma
Enhanced CVD)
- Photo CVD

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 CVD Chamber

Chamber type

Batch type
3 – ZONE FURNACE

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr