Thin Film Processing

Gary Mankey
MINT Center and Department of Physics
http://bama.ua.edu/~gmankey/
gmankey@mint.ua.edu

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 þacuum
þacuum ‡ A vacuum is defined as less
than 1 Atmosphere of pressure.
‡ 1 Atm = 105 Pa = 103 mbar =
760 Torr
760 mm Hg ‡ Below 10-3 Torr, there are more
ATM
gas molecules on the surface of
the vessel then in the volume of
the vessel.
‡ High þacuum < 10-3 Torr
‡ þery High þacuum < 10-6 Torr
‡ Ultra High þacuum < 10-8 Torr
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 :hy do we need a vacuum?

‡ Keep surfaces free of

contaminants.
j ‡ Process films with low density
of impurities.
‡ Maintain plasma discharge for
sputtering sources.
Mean free path for air at
20 ºC: ‡ Large mean free path for
j = 7 x 10-3 cm / P(mbar) electrons and molecules
(j = 1 m @ 7 x 10-5 mbar).

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þacuum Systems
‡ A vacuum system consists of
chamber, pumps and gauges.
‡ Chambers are typically made of
glass or stainless steel and
sealed with elastomer or metal
gaskets.
‡ Pumps include mechanical,
turbomolecular, diffusion, ion,
sublimation and cryogenic.
‡ Gauges include thermocouple
for 1 to 10-3 mbar and Bayard-
Alpert for 10-3 to 10-11 mbar.
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Alabama Deposition of Advanced Materials
‡ All materials are either
glass, ceramics, stainless
steel, copper and pure
metals.
‡ A turbomolecular pump
and a cryo pump create
the vacuum.
‡ Sputtering sources are
used for deposition.
‡ Characterization
methods include
RHEED, and Auger
electron spectroscopy.
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 Bayard-Alpert or Ionization Gauge
Filament Collector ‡ Electrons, e-, produced by the
e- n hot filament are accelerated
n Grid
through the grid acquiring
e- n
n I+
I+ sufficient energy to ionize
n
e- neutral gas atoms, n.
I+ 1 cm
‡ The ionized gas atoms, I+, are
e- n then attracted to the negatively,
n n biased collector and their
current is measured with an
-45 þ +150 þ electrometer.
Electrometer ‡ Typical ion gauges have a
6 þAC
sensitivity of 1-10 Amp / mbar
and range of 10-3-10-11 mbar.
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Residual Gas Analysis
‡ A quarupole mass spectrometer
analyzes the composition of gas
in the vacuum system.
‡ The system must be ³baked´ at
150 - 200 ºC for 24 hours to
remove excess water vapor from
the stainless steel walls.
‡ The presence of an O2 peak at
M/Q = 32 indicates an air leak.
‡ At UHþ the gas composition is
H2, CH4, H2O, CO and CO2.

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 Monolayer Time
Sticking Coefficient
S = # adsorbed / # incident
Impingement rate for air:
Z = 3 x 1020 j
 cm-2 s-1
Area of an adsorption site:
A Ë 1 Å2 = 10-16 cm2
‡ :e define the monolayer time as
the time for one atomic layer of gas
to adsorb on the surface:
o = 1 / (SZA).
‡ At 3 x 10-5 Torr, it takes about one
second for a monolayer of gas to
adsorb on a surface assuming a
sticking coefficient, S = 1.
‡ At 10-9 Torr, it takes 1 hour to form
a monolayer for S = 1.
‡ For most gases at room
temperature S<<1, so the
monolayer time is much longer.
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þapor Pressure Curves
‡ The vapor pressures of most
materials follow an Arrhenius
equation behavior:
PþAP = P0 exp(-EA/kT).
‡ Most metals must be heated to
temperatures well above 1000 K
to achieve an appreciable vapor
pressure.
‡ For PþAP = 10-4 mbar, the
deposition rate is approximately
10 Å / sec.
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 Physical Evaporation
‡ A current, I, is passed through
the boat to heat it.
Substrate
‡ The heating power is I2R, where
R is the electrical resistance of
the boat (typically a few ohms).
Flux
‡ For boats made of refractory
Boat Evaporant metals (:, Mo, or Ta)
temperatures exceeding 2000º C
can be achieved.
‡ Materials which alloy with the
High Current boat material cannot be
Source evaporated using this method.
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Limitation of Physical Evaporation

‡ Most transition metals, TM,

form eutectics with refractory
materials.
‡ The vapor pressure curves
show that they must be heated
to near their melting points.
‡ Once a eutectic is formed, the
boat melts and the heating
current is interrupted.

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 Electron Beam Evaporator
‡ The e-gun produces a beam of
electrons with 15 keþ kinetic
Substrate
energy and at a variable current of
up to 100 mA.
e-beam ‡ The electron beam is deflected
Flux
270º by a magnetic field, B.
Evaporant ‡ The heating power delivered to a
' small (~5mm) spot in the evaporant
Crucible is 15 kþ x 100 mA = 1.5 k:.
‡ The power is sufficient to heat
most materials to over 1000 ºC.
e-gun ‡ Heating power is adjusted by
controlling the electron current.
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 The Sputtering Process
Electrons (e-) are localized in the
plasma by a magnetic field.
Substrate The e- collide with argon gas
atoms to produce argon ions.
1 mTorr Ar The Ar+ are accelerated in an
+ Plasma electric field such that they strike
-

  Discharge the target with sufficient energy to

 

  eject target atoms.
Target The target atoms, being electrically
R R neutral, pass through the plasma
R and condense on the substrate.
Magnets

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 Measuring and Calibrating Flux
‡ Many fundamental physical properties are
sensitive to film thickness.
‡ In situ probes which are implemented in
the vacuum system include a quartz crystal
Ë microbalance, BA gauge, Auger / XPS,
and RHEED.
‡ Ex situ probes which measure film
thickness outside the vacuum system
include the stylus profilometer,
spectroscopic ellipsometer, and x-ray
diffractometer.
‡ Measuring film thickness with sub-
angstrom precision is possible.
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 Quartz Crystal Microbalance
Frequency Conversion to ‡ The microbalance measures a shift
Measurement Thickness in resonant frequency of a
vibrating quartz crystal with a
Display precision of 1 part in 106.
‡ fr = 1/2O sqrt(k/m) Ë f0(1-
m/2m).
Substrate ‡ For a 6 MHz crystal disk, 1 cm in
diameter this corresponds to a
Quartz change in mass of several
Crystal nanograms.
‡ d = m / (A), so for a typical metal
d Ë 10 ng / (10 g/cm3*1 cm2) =
Flux
0.1 Angstroms.
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 Auger / XPS
Electron Energy ‡ An x-ray source produces
Analyzer
photoelectrons or a electron gun
produces Auger electrons.
Excitation:
‡ The electrons have kinetic
X-rays or
keþ Electrons energies which are characteristic
of the material.
‡ The attenuation of substrate
Photoelectrons & electrons by the film is described
Auger Electrons by Beer¶s law:
I = I0 exp(-dcosã/ ).
‡ Since, Ë 10 Å, this technique
has a high sensitivity.
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 Auger Electron Spectroscopy
Kinetic ‡ The excitation knocks a core
Energy electron out producing a core hole.
Excitation ‡ To lower the energy of the ion, an
electron from an upper shell decays
EþAC
nonradiatively into the core hole.
Upper
Shell ‡ The Auger electron from the upper
shell acquires an energy equal to the
energy difference of the core hole
and upper shell.
Core ‡ The kinetic energy of the electrons
Hole are measured to identify the
chemical species of the atoms.
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Secondary Electron Energy Distribution

‡ The energy distribution is

characterized by
± An elastic peak at the
incident electron energy.
± A low energy peak which
increases as 1/E2 and drops
off rapidly below 10 eþ.
± Auger electrons, which can
be measured to determine
chemical composition.

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Cu Auger Scan in Pulse Counting Mode

‡ These transitions
correspond to Auger
electrons ejected from the
valence band by a
neighboring electron
filling the L shell or 2p
levels.

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Cu Auger Spectrum for Analog Mode

‡ In analog mode, the

analyzer energy is
modulated and a lock-in
amplifier detects the
derivative of the number
of electrons or dN(e)/dE
vs. E.
‡ The high energy peaks
correspond to those on the
previous slide.
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The Universal Curve for

‡ The Universal Curve describes the

dependence of electron mean free
path, , on energy for most
materials.
‡ In most cases, it is accurate to
within a factor of two.

= (35 / E)2 + 0.5
E

with in Å and E in eþ.

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 Reflection High-Energy Electron Diffraction
‡ 15 keþ electrons reflect from the
surface and are displayed as a spot
on a phosphor screen.
d = atomic
spacing ‡ The angle is adjusted such that
s electrons reflecting from adjacent
layers interfere destructively.
15 keþ ‡ :hen only one layer is exposed, the
Electron Gun Screen spot is bright.
‡ :hen the top layer covers half of
the surface, the spot is extinguished.
Path difference = 2dsinã = (n+1/2) j
‡ The time between two maxima in
j = [150 / E(eþ)]1/2 the intensity plot is the monolayer
time.
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 Epitaxial Growth

‡ Epi-Taxi (@


epi meaning ³on´
Film taxi meaning ³arrangement
in relation to a source of
stimulation´
‡ The crystal structure of the
film has a direct relationship
Substrate to that of the substrate

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 Growth Modes for Ultrathin Films
‡ The growing film surface can
exhibit different behaviors
depending on substrate
Layer by Layer Stranski-Kastranov temperature, interfacial
strain, and alloy miscibility.
‡ The growth modes must be
þolmer-:eber Diffusion Limited characterized using a
combination of chemical
tools such as Auger electron
spectroscopy and structural
tools such as RHEED and
Surface Segregation Surface Alloy
atomic force microscopy.
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