INTRODUCTION

TO THIN FILMS
LABORATORY
BY
DR. EMAN A. GAML
LECTURER OF EXPERIMENTAL PHYSICS

1
 WHAT ARE THIN FILMS?

• A THIN FILM IS A LAYER OF MATERIAL ITS THICKNESS RANGING FROM

FRACTIONS OF A NANOMETER (MONOLAYER) TO SEVERAL
MICROMETERS IN THICKNESS.

2
METHODS OF FABRICATING THIN FILMS
• THERMAL EVAPORATION TECHNIQUE
• PHYSICAL VAPOR DEPOSITION
• CHEMICAL VAPOR DEPOSITION
• ELECTRODEPOSITION
• LANGMUIR-BLODGETT
• SOL-GEL METHOD
• SPUTTERING

3
Physical vapor deposition (PVD): evaporation and sputtering
In PVD, chemical reactions are not involved, except for reactive (add reactive gases into
chamber) evaporation or reactive sputter deposition, which are not widely used.

Evaporation:
• Material source is heated to high temperature in vacuum either by thermal or e-
beam methods.
• Material is vapor transported to target in vacuum.
• Film quality is often not as good as sputtered film (that involves energetic
bombardment of ions to the as-deposited film, which makes the film denser).
• The film thickness can be monitored precisely using a quartz balance – this is
necessary as the deposition is not reproducible (tiny change in T leads to large
change of deposition rate. T is not monitored, power is).

Sputter deposition: (there is also sputter etching)

• Material is removed from target by momentum transfer.
• Gas molecules are ionized in a glow discharge (plasma), ions strike target and
remove mainly neutral atoms.
• Sputtered atoms condense on the substrate.
• Not in vacuum, gas (Ar) pressure 5-50mTorr.
4
 Evaporation (also called vacuum deposition)
• In evaporation, source material is heated in high
vacuum chamber (P < 10-5 Torr), hence the name
vacuum deposition.
• High vacuum is required to minimize collisions of Wafer holder
source atoms with background species (light of site
Wafers
deposition)
• Heating is done by resistive or e-beam sources.
• Surface interactions are physical, can be very fast Atomic
flux
(>1m/min possible, but film quality may suffer. For
R&D typical 0.1-1nm/sec).
Vacuum Source material
• High sticking coefficient (at low T, adatom stays Heater (resistance
or E-beam)
wherever it hits with limited surface migration),
leading to poor conformal coverage/significant
shadow. But this also makes evaporation the most
Vacuum system
popular thin film deposition for nanofabrication Exhaust

using liftoff process.

• Deposition rate is determined by emitted flux and by geometry of the source and wafer.
• Evaporation is not widely used by industry – sputter deposition is.
5
• For microfabrication R&D, evaporation is as important as sputter deposition.
 Evaporation: vacuum pressure and mean free path

Assume a particle of diameter s, moving in speed v. wafer

Collision cross-section = s2
Collision volume swept during dt = s2 vdt
# of collisions during dt = (n/V) s2 vdt
Here n/V is number density.
Average mean free path  = vdt/# = [(n/V) s2]-1 v

In more rigorous treatment, (PV=nkT)

2s
n kT
  ( s 2 2 ) 1  source
V 2s 2 P
Assume s = 3Å, T= 300K
If =30 cm, then a pressure <2.6x10-4 Torr
P(Torr)  (cm) = 7.8x10- is required.
3
Typical vacuum for evaporation <5106 -6Torr
1Torr = 1mmHg = 1/760atm
Mean-free path of varied gases

7
 Influence of background vacuum pressure
Time to form a single complete layer
of gas on a surface, assume sticking
coefficient = 1.

Pressure (Torr) Time

10-4 0.02 s
10-5 0.2 s
10-6 2s
10-7 20 s
1bar=100000Pa (1atm=1.013bar)
1mbar=100Pa 10-8 3 min
1Torr=100000/760=132Pa=1.32mb
ar 10-9 35 min
10-10 6 hr
8
10-11 3 days
 Arrival ratio

Arrival ratio:
Ratio of molecular vapor arrival at
1nm/sec deposition rate to
molecular impact of residual gas.

Arrival ratio = 1 means the number of film molecules hitting the surface per second is the
same as the number of gas molecules.
For materials that is very reactive with the gas (such as Ti to O2), the film can be very
impure when arrival ration 1.
9
In fact, Ti is used as a pump for ultrahigh vacuum (called Ti pump, where Ti vapor is
produced to trap gas in vacuum chamber).
Evaporation characteristics of materials

10

. From “Materials science of thin films” by Ohring, 2002.

Photos of source material for evaporation

11
 Types of evaporation according to heating method
Three types:
Thermal evaporator – resistive heating, the only choice for
evaporation of organic material.
Electron beam evaporator – heated by electron beam, most popular,
more expensive than thermal evaporator.
Inductive heating (must be unpopular).

Inductive heating:
Metal element is wound around crucible and RF power is run
through coil.
RF induces eddy currents in the charge causing it to heat.
Eddy current is caused when a conductor is exposed to a
changing magnetic field due to relative motion of the field
source and conductor; or due to variations of the field with
time.
These circulating current create induced magnetic fields that
oppose the change of the original magnetic field due to Lenz's
law, causing repulsive or drag forces between the conductor
12
and the magnet.
Thermal evaporation
Widespread use for materials whose
vapor pressure can be reasonable at
1600oC or below.
Common evaporant materials:
Au, Ag, Al, Sn, Cr, Sb, Ge, In, Mg, Ga;
CdS, PbS, CdSe, NaCl, KCl, AgCl, MgF2,
CaF2, PbCl2.

13
EDWARDS THERMAL EVAPORATION
SYSTEM IN DAMIETTA UNIVERSITY

14
 Electron beam evaporation

Deflection plates are to raster scan

the beam across charge surface.

• Using a focused electron beam to heat and evaporate metals, electron temperature can be
as high as 10,000 K. Electrons are accelerated by DC 10kV, and current 10s-100s of mA.
• Suitable for high Tmelt metals like W, Ta, …
15
• Evaporation occurs at a highly localized point near the beam bombardment spot on the
source surface , so little contamination from the crucible (not hot, water cooled).
Can one do e-beam evaporation of insulating materials like SiO2?
Photos of e-beam evaporator
Mechanical shutter:
Evaporation rate is set by temperature of
source, but this cannot be turned on and
off rapidly.

Cooling water Shutter

Heat conduction of the hearth

Put crucible
limits achievable temperature.
here
Power density: 10kV, up to 1.5A,
0.2-1cm2  15-75kW/cm2.16
 Comparison of thermal and e-beam evaporation

Thermal evaporation:
• Simple, robust, and in widespread use.
• Use W, Ta, or Mo filaments to heat evaporation source.
• Typical filament currents are 200-300 Amperes.
• Exposes substrates to visible and IR radiation.
• Contamination from heated boat/crucible.
Electron beam evaporation:
• More complex, but extremely versatile, virtually any material.
• Less contamination, less heating to wafer (as only small source area heated to very high T).
• Exposes substrates to secondary electron radiation. 17
• X-rays can also be generated by high voltage electron beam.
• Since x-rays will damage substrate and dielectrics (leads to trapped charge), e-beam evaporators
cannot be used in MOSFET.
Popular heating “containers” for evaporation source

Resistors (put source rod inside coil) Heating boat (open top)

Crucibles Box with small opening

18
(only choice for e-beam evaporator) (Knudsen cell!)
 Typical boat/crucible material

Considerations: thermal conductivity, thermal expansion, electrical conductivity, wetting

and reactivity.
Graphite crucible is most popular, but avoid cracking the crucible due to stress/
temperature gradients (bad for materials that “wet” graphite such as Al and Ni). 19
Aluminum: tungsten dissolves in aluminum, so not quite compatible.
 How to monitor film thickness during evaporation?
6MHz

Quartz
Electrode

Deposited
film Vapor

Quartz Crystal Micro-balance (QCM): (similar idea to quartz clock)

• Quartz is a piezoelectric material.
• With a high frequency AC voltage activation, the amplitude of vibration is maximum at
resonance frequency.
• This resonance frequency will shift when film is deposited on its surface. 20
• Thus by measuring frequency shift f, one can measure film thickness with sub-Å accuracy.
http://en.wikipedia.org/wiki/Quartz_crystal_microbalance
 SPUTTERING
• SPUTTERING OCCURS WHEN THE ION IMPACT ESTABLISHES A TRAIN
OF COLLISION EVENTS IN THE TARGET LEADING TO THE EJECTION OF
A MATRIX ATOM.

TYPES OF SPUTTERING:
• DC SPUTTERING
• RF SPUTTERING
• REACTIVE SPUTTERING
• MAGNETRON SPUTTERING
• BIAS SPUTTERING
21
 • ”FORMATION OF AN OXIDE NETWORK THROUGH POLYCONDENSATION
REACTIONS OF A MOLECULAR PRECURSOR IN A LIQUID.”
• A SOL (SOLUTION) IS A STABLE DISPERSION OF COLLOIDAL PARTICLES OR
POLYMERS IN A SOLVENT. THE PARTICLES MAY BE AMORPHOUS OR
CRYSTALLINE. AN AEROSOL IS PARTICLES IN A GAS PHASE, WHILE A SOL IS
PARTICLES IN A LIQUID,
• A GEL CONSISTS OF A THREE DIMENSIONAL CONTINUOUS NETWORK,
WHICH ENCLOSES A LIQUID PHASE, IN A COLLOIDAL GEL, THE NETWORK IS
BUILT FROM AGGLOMERATION OF COLLOIDAL PARTICLES. IN A POLYMER GEL
THE PARTICLES HAVE A POLYMERIC SUB-STRUCTURE MADE BY AGGREGATES

SOL-GEL
OF SUB-COLLOIDAL PARTICLES. GENERALLY, THE SOL PARTICLES MAY INTERACT
BY VAN DER WAALS FORCES OR HYDROGEN BONDS. A GEL MAY ALSO BE
FORMED FROM LINKING POLYMER CHAINS. IN MOST GEL SYSTEMS USED FOR
METHOD MATERIALS SYNTHESIS, THE INTERACTIONS ARE OF A COVALENT NATURE AND
THE GEL PROCESS IS IRREVERSIBLE. THE GELATION PROCESS MAY BE
REVERSIBLE IF OTHER INTERACTIONS ARE INVOLVED.
• •THE IDEA BEHIND SOL-GEL SYNTHESIS IS TO “DISSOLVE” THE COMPOUND IN
A LIQUID IN ORDER TO BRING IT BACK AS A SOLID IN A CONTROLLED
MANNER.
• •MULTI COMPONENT COMPOUNDS MAY BE PREPARED WITH A CONTROLLED
STOICHIOMETRY BY MIXING SOLS OF DIFFERENT COMPOUNDS.
• •THE SOL-GEL METHOD PREVENTS THE PROBLEMS WITH CO-PRECIPITATION,
WHICH MAY BE INHOMOGENEOUS, BE A GELATION REACTION.
• •ENABLES MIXING AT AN ATOMIC LEVEL. 22
•RESULTS IN SMALL PARTICLES, WHICH ARE EASILY SINTERABLE