Physical Vapor Deposition (PVD)

Vacuum evaporation
 Vacuum evaporation
• Material is heated to attain gaseous state
• Carried out under high vacuum (10-7 torr, or 10-4 ~10-5Pa)

• Advantages
– Films can be deposited at high rates (~0.5 µm/min)
– Low energy atoms (~0.1 eV) leave little surface damage
– Little residual gas and impurity contamination due to high vacuum
– No substrate heating
– Inexpensive

• Limitations
– Difficult to control alloy compounds
– Poor step coverage
– Nonuniformity of coverage over wafer or multiple wavers

Resistive heating evaporation

• Simple, Robust, Inexpensive

• Can only reach temperatures of 1800 °C

• Uses W, Ta, or Mo filaments to heat sources

• Typical filament currents are 200-300A

• Exposes substrate to visible and IR radiation

• Typical rates are 0.1-2 nm/sec

• Materials

– Au, Ag, Al, Sn, Cr, Ti, Cu

 Evaporation system requirements

• Vacuum:
– 10-6 torr for medium quality films
• Cooling water
– Hearth
– Bell Jar
• Mechanical Shutter
– Evaporation rate is set by temperature of source, can
not be turned on and off rapidly. A mechanical shutter
allows control of start and stop times.
• Electrical Power
– Either high current or high voltage: typically 1-10kW

Evaporation support materials

• Metals
– Tungsten (W): MP = 3380°C
– Tantalum (Ta): MP = 3000 °C
– Molybdenum (Mo): MP = 2620 °C

• Ceramics
– Graphitic Carbon (C): MP = 3700 °C
– Boron Nitride (BN): MP = 2500 °C
– Alumina (Al2O3) MP = 2030 °C
 Resistive heating elements

Electron beam heated evaporation source

 Electron beam properties
• More complex than resistive heating but extremely
versatile
• Can achieve temperatures > 3000°C
• Uses evaporation crucibles in a copper hearth
• Typical emission voltages: 8-10 kV can produce
x-rays
• Typical deposition rates 1-10 nm/sec
• Evaporant Materials:
– Everything resistance heating uses plus
– Ni, Pt, Ir, Rh, Ti, V, Zr, W, Ta, Mo
– Al2O3, SiO, SiO2,SnO2, TiO2, ZrO2

Adsorption

• Adsorption is the sticking of a particle to the surface

• Physisorption:
– The impinging molecule loses kinetic energy to thermal
energy within some residence time, and the lower energy of
the molecule does not allow it to overcome the threshold that
is needed to escape

• Chemisorption:
– The impinging molecule loses its kinetic energy to a
chemical reaction which forms a chemical bond between it
and other substrate atoms.
 Condensation

• The molecules impinging on the surface may:

– Adsorb and permanently stick where they land (rare)
– Adsorb and diffuse around the surface to find an
appropriate site
– Adsorb and desorb after some residence lifetime.
– Immediately reflect off the surface

• Incident vapor molecules normally have a kinetic energy

much higher than kT of the substrate surface

• Whether they stick depends on how well it can equilibrate

with the substrate surface giving up enough energy so that
it does not have enough to escape

Condensation control

• Control of condensation of the evaporant is achieved

through control of the substrate temperature

• Higher substrate temperature

– Increases thermal energy of adsorbed molecules
– Shortens the residence time
– Increases surface diffusivity of adsorbed molecules
– Performs annealing of deposited film

• Substrate heaters
– IR lamps from frontside
– Heater coils from backside
 Kinetic theory of gases
• PV=nRT n=PV/RT concentration of gas
• At STP n ~ 2.7 x 1019 molecules/cm3
• Standard pressure
– 1 atm = 760 mmHg = 760 torr = 1.013 x 105 Pa
• Mean Free Path (λ): mean distance a molecule
travels before colliding with another molecule

λ= kT
2πpd 2
= 0.707
πd 2 n

– for 10-4 Pa λ = 60m

– Line of sight travel no collisions

Flux
• Can calculate the bombardment rate of molecules on the surface
(Flux) # of molecules per area per second
• Used to estimate the deposition rate

P 2.63 ×10 20 P
Φ= = (molecules / cm 2 ⋅ sec)
2πmkT MT

M: molecular weight N s N s 2πmkT

P: Pressure (Pa) t= =
Φ P
T: Temp in Kelvin
K: Boltzman Coef. assumes each molecule sticks
m: mass of molecule t: time to form monolayer
Pressure : P Ns: surface density (molecules/cm2)
 Evaporation Source Position

Molecular Beam Epitaxy (MBE)

™ Insert sample
and heat
material
sources
™ Open shutters
™ Monitor
condensation
and
sublimation
™ Close
shutters
™ Remove
sample
 Molecular Beam Epitaxy (MBE)

Molecular Beam Epitaxy (MBE)

™ Actually Evaporation, not CVD
™ Requires Ultra-High vacuum (10-10 torr)
™ Shuttered effusion cells contain very pure samples of
the target material.
™ Shutters are opened and exposed to an electron beam
which vaporizes the target material.
™ Wafer surface is heated to promote epitaxial film
growth.
™ Wafer is rotated to improve uniform film growth.
™ MBE allows for the creation of very specialized devices:
- mono-atomic sandwiched layers are possible
™ A favorite toy of research laboratories, but is also used
in the mass-production of gallium arsenide devices.
 Physical Vapor Deposition (PVD)
-- Sputtering
• Uses high energy particles (plasma) to dislodge atoms
from source surface
• Carried out in low-medium vacuum (~10-2 torr)
• Advantages
– Can use large area targets for uniformity of film
– Easy thickness control via time
– Easy to deposit alloys and compounds
– Good step coverage
– No x-ray damage

Sputter Station

• Magnetic field used to confine plasma and electric field used to

accelerate
• DC plasma used for conductive metals
• RF plasma used for nonconductive dielectrics
• Several targets can mix or due layers without breaking vacuum
 Sputter Deposition Systems

E RF Sputter System

DC Sputter Deposition Magnetron Sputter Deposition

Physical Vapor Deposition (PVD)

-- DC Sputtering
• Uses plasma to sputter target, dislodging atoms which
then deposit on wafers to form film.
• Higher pressures than evaporation - 1-100 mtorr.
• Better at depositing alloys and compounds than
evaporation.
 Physical Vapor Deposition (PVD)
-- RF Sputtering
• For DC sputtering, target electrode is conducting.
• To sputter dielectric materials use RF power source.

• Due to slower mobility of ions vs. electrons, the plasma biases

positively with respect to both electrodes. (DC current must be zero.)
∴ continuous sputtering.
• When the electrode areas are not equal, the field must be higher at the
smaller electrode (higher current density), to maintain overall current
continuity

Physical Vapor Deposition (PVD)

-- RF Sputtering
• Thus by making the target electrode smaller,
sputtering occurs "only" on the target. Wafer
electrode can also be connected to chamber
walls, further increasing V1/V2.

• The wafer electrode can be separately biased

(RF), which allows cleaning or controlled
sputtering of the wafer with Ar+ ions (bias-sputter
deposition).

• This can allow more conformal deposition

because the ions are highly nondirectional and
sputter selectively.
Comparison of evaporation and sputtering
EVAPORATION SPUTTERING

Low energy atoms High energy atoms

High vacuum path Low vacuum, plasma path
• Few collision • Many collision
• Line-of-sight deposition • Less line-of-sight deposition
• Little gas in film • Gas in film
Larger grain size Smaller grain size
Fewer grain orientations Many grain orientations
Poorer adhession Better adhession

Pulsed Laser Deposition System

Target: metals, semiconductors…

Laser: UV, 10 ns pulses
Vacuum: Atmospheres to ultrahigh vacuum
Film thickness: typically 100-200 nm.
Deposition rate: 0.1 nm/pulse
http://www.physandtech.net/
 Advantages of Pulsed Laser Deposition

• Flexible, easy to implement

• Growth in any environment
• Exact transfer of complicated materials (YBCO)
• Variable growth rate
• Epitaxy at low temperature
• Resonant interactions possible (i.e., plasmons in metals,
absorption peaks in dielectrics and semiconductors)
• Atoms arrive in bunches, allowing for much more controlled
deposition
• Greater control of growth (e.g., by varying laser
parameters)

Disadvantage:
™ Uneven coverage
™ High defect or particulate concentration
™ Not well suited for large-scale film growth
™ Mechanisms and dependence on parameters not well understood

PLD with ultrafast (<1 ps) pulses

20 ns EXCIMER versus 1 ps TJNAF-FEL

Cobalt ~20 mJ/pulse, 20 ns, 308 nm, Steel, ~20 μJ/pulse, 18 MHz, 3.1 micron
25 Hz, 1 x 10-5 Torr 1 x 10-2 Torr, 60 Hz pulsed, rastered beam

Less melting!
TARGET
(deposited on silicon)

Few
particulates!
for Nb: < 1 per cm-2
FILM
 Optimization of PLD Parameters

™ PLD technique is one of the most popular and effective

techniques used in the present days for the deposition of thin
films. In this technique, a pulsed laser is directed on a solid
target. The nanosecond laser pulse is focused to give an
energy density sufficient to vaporize a few hundred
angstroms of surface material in the form of neutral or ionic
atoms and molecules with kinetic energies of a few eV, which
then get deposited onto the substrate.

™ The plasma temperature is high (~ 103 K) and the evaporants

become more energetic when they pass through the plume.
This affects the film deposition in a positive manner due to
increase in the adatom surface mobility.

™ Use of short pulses helps to maintain high laser power

density in a small area of the target and produces congruent
evaporation.

™ Deposition parameters: substrate temperature, laser fluence,

pulse repetition rate, and target substrate distance.

Glancing Angle Deposition (GLAD)

倾斜角沉积技术

GLAD UHV deposition system

Kevin Robbie et al.,

J. Vac. Sci. Technol. A15 (1997) 1460; B16 (1998) 1115.
Rev. Sci. Instrum. 75 (2004) 1089.
 Glancing Angle Deposition (GLAD)

GLAD is based on thin film deposition, by evaporation or sputtering, and employs

oblique angle deposition flux and substrate motion to allow nanometer scale control
of structure in engineered materials.

Glancing Angle Deposition (GLAD)

Stationary substrate

Tangent rule: tan(β) = (1/2) tan (α) (when α is small; poor when α > 50º)
(Nieuwenhuizen and Haanstra, Philips Tech. Rev. 27 (1966) 87.)
Tait relationship: β = α –asin ((1-cos(α))/2) (when α is large)
(Tait, Smy, Brett, Thin Solid Films 226 (1993) 196.)
 Glancing Angle Deposition (GLAD)

Staionary substrate, one evaporation source, Cr films

Glancing Angle Deposition (GLAD)

Stationary substrate, two evaporation sources, SiO2 films

Independent control of column angle and film porosity. The porosity is constant, the
column angle β is controlled between the inclined and vertical angles.
 Glancing Angle Deposition (GLAD)

Various nanostructures obtained in GLAD thin films

Glancing Angle Deposition (GLAD)

Various nanostructures obtained in GLAD thin films

 Glancing Angle Deposition (GLAD)

the direction of arrival

flux arrived from of the flux was
the right for the alternated from the
entire deposition left and right 12 times
during deposition

the substrate a combination of the

was rotated techniques used in b)
continuously and c). The substrate
during deposition was rotated in 90
degree steps during
deposition.

GLAD is based on thin film deposition, by evaporation or sputtering, and employs

oblique angle deposition flux and substrate motion to allow nanometer scale control
of structure in engineered materials.
h = c1 (ηU / ρg )1/ 2
h: film thickness;
U: substrate speed;
η: liquid viscosity;
ρ: liquid density;
c1: ~0.8 for Newtonian liquid

When U and η are not high enough, h = 0.94(ηU ) 2/3 /γ LV

1/6
( ρg )1/ 2
h(t ) = h0 /(1 + 4 ρω 2 h0 t / 3η )1 / 2 ρ: liquid density;
2 h0: initial thickness; t: time
ω: angular velocity; η: liquid viscosity;

hfinal = (1 - ρ A /ρ A ° )( 2 ρ3ηmω 2 )1/ 3 t final = t spin -off + h spin -off ρ A ° /mρ A

A°
Nonhydrolytic Sol-gel
Nonhydrolytic Sol-gel