Industrial Thin Film Technologies

Andrei I. Mardare

Institut für Chemische

Technologie Anorganischer Stoffe
Physical methods: Physical Vapor Deposition (PVD)

 Thermal evaporation

thermal evaporation sources, design, MBE, JVD

 Pulsed laser deposition

design, film characteristics

 Energy beams and plasma

electron beam evaporation, lithography

 Sputtering

planar diode, DC sputtering

Course Outline
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Thermal evaporation
 Joule effect is used for heat generation in furnaces - evaporation sources in vacuum
 evaporation sources (thermal elements)
 high melting point metals (W, Ta, Mo, and their alloys)
 direct evaporation
 the material to be evaporated comes in direct contact with the thermal element
 risk of alloying between the thermal element and the material - short lifetime
 indirect evaporation - the thermal element is used for heating a crucible (e.g. Al2O3)

Thermal  point source  loop source  small amounts of material

filaments  for wire materials
 low deposition temperatures
 coils  baskets
 average amounts of
material (mg)
 for small flakes, pellets
 serpentines
 higher deposition
 spirals temperatures possible

Evaporation sources
www.lesker.com 4
Thermal boats  dimple  top hat  long through

 notched  canoe

Thermal boxes  single or multiple reservoirs for plane source simulation

Rod sources (Cr on W)

 high amounts of material

 high deposition rates

Evaporation sources  high temperatures

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Coated thermal elements (alumina)
 inverted hat
 basket  interaction with the thermal
element is minimized
 alloying is avoided
 lifetime is extended

Crucibles - heated by coils or baskets

 alumina  quartz C  Ta, Mo, W  boron nitride

 used when indirect deposition sources are necessary

 evaporated material should not alloy (or diffuse into) with the crucible
 e.g. Al suitable for deposition from alumina or W, but not from C
Evaporation sources
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 designs of single or multiple sources are possible

 two highly conductive electrodes (pure Cu) are used for transporting high currents (300A DC
or AC) to the thermal element
 cooling of the current feedthroughs is necessary
 liquid (the inner part of the rods is hollow) or air (outside the chamber ventilators are
used for cooling the entire rod)

Thermal evaporator design

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 most of the time, thermal / evaporation shielding has to be used for protecting the chamber

1) pumping unit 3) power source

2) pressure measurement 4) vacuum chamber with implosion protection

Thermal evaporator design
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 Substrate

deformed image diffraction effects at the edges

Substrate

shadow mask

source source

Line-of-sight deposition
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 glass PEN PET PI
(a) (b) (c) (d)

200 nm 200 nm 200 nm 200 nm

1 µm 1 µm 1 µm 1 µm

0 nm 12.5 nm 25 nm

Thermal evaporation of Al on various substrates

A.I. Mardare, et. al., Phys Stat Solidi A 209 (2012) 813 10
 Al (111)

Al (111)

Thermal evaporation of Al on various substrates

A.I. Mardare, et. al., Phys Stat Solidi A 209 (2012) 813 11
  sublimation sources  liquid sources
 Ca, C, Cr, Mg, Mn, Pd, Ti, Mo, Fe, Si, etc.  Cu, Au, Ag, Sn, Pt, Rh, W, etc.

 evaporation rule of thumb:

 melt is required if the evaporant does not achieve a minimum vapor pressure of 10-3 mbar
at its melting temperature

 alloy sources
 in the gas phase, the alloy may decompose
 due to different vapor pressure of single elements,
the stoichiometry of the film will be different from
the stoichiometry of the source
 co-evaporation from the single sources is more
efficient for forming film alloys
 the precise stoichiometry can be achieved
controlling the individual evaporation rates

Evaporation from different sources

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 cheapest PVD method for thin film deposition

 high evaporation rates are possible - low evaporation rates are difficult

 not the first choice for deposition of alloy thin films - not impossible, though

 extra energy is usually transmitted to the substrate by radiation - not necessarily desirable

 large areas are easily covered - efficient industrial method for coatings

 uniform layers can be obtained by rotating the substrate off-axis

 efficient for metals with average melting/sublimation temperatures (< 1500°C)

 line-of-sight deposition method - shadow masks can be used for substrate patterning

 typical atomic kinetic energy - 0.1 eV

 cos exponent = 2 - 4
Thermal evaporation - features
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Molecular beam epitaxy
MBE
 Epitaxy = the film has the same structure as the substrate

 homoepitaxy - e.g. Si film deposited on Si substrate

 heteroepitaxy - the film has a different lattice than the

substrate and the missmatch will accommodate by elastic strain

film

substrate

Epitaxy
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 Molecular beam = stream of identical molecules with identical kinetic energies (moving with
equal velocities) non-interacting with each-other
 shadowing effects should be kept at a minimum - very low evaporation rates required

 MBE = epitaxy with a molecular beam usually in a layer-by-layer approach

 use in electronic industry for depositing single crystals (Ga, As)
 precise control of multilayer structures - electron confinement in space
 quantum dots or wells - critical for modern semiconductor devices

 deposition rates usually < 0.3 nm s-1 - approx. 1 atomic layer every second
 slow rates promote epitaxy due to the longer time available for surface diffusion before
the next atomic layer deposits

 ultra-pure films can be easily produced - UHV systems have to be used

 Knudsen cells are used as thermal sources for MBE

MBE
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 Knudsen cell = thermally stabilized recipient (crucible)
containing vapors in equilibrium
 a small opening (aperture) allows the molecular
beam to form
 diameter of the aperture affect the deposition rates
 the molecules are ejected due to the pressure
difference between the vapor pressure inside the
cell and the background pressure in the vacuum
system (UHV)

 water cooling is necessary for avoiding extra heating of

the surrounding
Knudsen cells
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 a shutter is always used - thermal stability must be reached inside the cell before the deposition
starts (the beam is uniform and the impingement flux is constant)

 MBE systems usually have

more than 3 Knudsen cells
(possibly operating in the
same time)
 big vacuum systems
 very “shiny” and expensive

Knudsen cells
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 various sizes are available for K-cells, usually defined by the crucible volume

 mini K-cells are usually mounted in

CF40 flange (for UHV)
 low power needed 
 low crucible volume 

 hot-lip K-cell - the outer rim of the cell is hot for

avoiding condensation of material during evaporation
 most metals, Ga, In

 cold-lip K-cell - the outer rim of the cell is cooled for

avoiding the molten evaporant to wet the upper part of
the crucible - used for Al
 Al tends to creep out of the crucible
Knudsen cells
www. tectra.de 19
 substrate = Al thin film on glass

Au nanoparticles by MB deposition
A.I. Mardare, et. al., J Phys Chem C 113 (2009) 3105 20
 Al background anodization is affected by the presence of Au nanoparticles

Surface modification by MB deposition

A.I. Mardare, et. al., J Phys Chem C 113 (2009) 3105 21
 Fine tuning of composite oxide properties as a function of Au nanoparticle sizes
 the anodic growth and dielectric properties of the oxides are easily modified

Surface modification by MB deposition

A.I. Mardare, et. al., J Phys Chem C 113 (2009) 3105 22
Surface modification by MB deposition
A.I. Mardare, et. al., J Phys Chem C 113 (2009) 3105 23
 Zone 3 - crystallization
Zone 2 - mixing

Zone 1 - efusion

 single crystals are developed at nanometer scale - monocrystalline films

 III-V compounds (GaAs, AlAs, InP, etc.)
 II-VI compounds (CdSe, ZnS, CdTe, etc.)

MBE from multiple sources - three zone cell design

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  composite electro-active polymer films
 vapor phase mixing of polymer and metal (Au)

 Au grain in thin polypropilene film

Metal-polymer composite films

S.A.Y. Al-Ismail, et. al., J Phys E 20 (1987) 344 25
 expensive chamber systems usually necessary - UHV or XHV for high purity films

 very low evaporation rates are possible

 co-deposition from multiple sources is possible - three zone design

 controlled doping is possible due to low evaporation rates

 relatively large areas are easily covered - Si wafer technology in semiconductor industry

 uniform layers can be obtained by rotating the substrate off-axis

 line-of-sight deposition method - shadow masks can be used for substrate patterning

 typical atomic kinetic energy - 0.1 eV

 cos exponent = 2 - 4

MBE - features
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Jet vapor deposition
JVD
 Jetgal® ArcelorMittal automotive – Zn deposition
 H-free coating process
 environmentally friendly
 suitable for any metallurgy – all ultra high
strength steels can be coated by JVD
 JVD does not change the initial
roughness of the substrate

 The Zn coating obtained is of very high

purity. The absence of heat treatment during
the coating process enables Jetgal®
coatings to be offered without restriction on
virtually all the steel grades developed by
ArcelorMittal for the automotive industry.
Jet vapor deposition
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 usual Zn thickness: 5 - 7.5 µm
 JVD Zn coating is ductile, enabling it to withstand high rates of deformation
 Suitable surface preparation prior to JVD ensures coating adhesion

Jet vapor deposition

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 Corrosion - JVD coatings offer excellent corrosion protection, even when
damaged (impact, scratches, stone chips), due to the sacrificial
electrochemical behavior of zinc relative to iron.

 Drawing - JVD coatings have excellent intrinsic formability, making them

suitable for the most severe drawing operations. The tribological behavior of
Jetgal® coatings is slightly inferior to that of hot-dip coatings.

 Welding - Jetgal® steels have a wide resistance spot weldability range suited
to industrial requirements – automotive industry

JVD applications
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 Adhesive bonding - JVD films show good adhesive bonding behaviour:
good adhesive and mastic adhesion to the coating, good adhesion of the
coating to the metal and cohesion of the coating itself. The type of adhesive,
jointing conditions, as well as the nature of the protective oil and any
chemical treatment that may have been performed remain the factors with the
greatest influence on bonding quality.

 Versatile surface treatment - Jetgal® products coated on one or both sides

can be phosphated and painted using all current phosphating and paint
processes.

JVD applications
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