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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Pulsed Laser Deposition
PLD
… sometimes PLA
 PLD uses a laser beam to ablate the surface of a target and a
film is formed by ablated vapor condensation on a substrate
 film formation can also be a reactive process when a
reactive gas is dosed inside the chamber - e.g. oxide
formation using O2 and metallic targets

 the collision frequency between plasma species

increases with the increase of the reactive gas pressure
 condensations among molecular and atomic
species lead to formation of clusters with sizes
ranging from dimers to submicron particles
 the cluster concentration in the plume increases
with the background (gas) pressure and with the
distance to the substrate (longer flying time)

 even though the PLD is one of the most simple experimentally technique for thin film fabrication,
its ablation mechanism is the most sophisticated among all PVD methods
 most of the time a trial-and-error approach gives faster results as compared with
complicated calculations for estimating the final properties of a PLD film
PLD
4
 PLD is also know as pulsed laser ablation (PLA) target

 various deposition geometries are used plume

off-center configuration
conventional configuration
with substrate rotation substrate

substrate holder

off-axis configuration
reverse face configuration shadow mask configuration

PLD geometries
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 in conventional configuration of PLD the target and sample
face each other
 usually the target is rotated during the
ablation for ensuring an uniform material
removal from the target surface
 since the substrate faces the target, all
removed atoms, molecules, clusters and
droplets due to splashing will be collected
on the substrate forming the thin film

UV laser

 useful for materials where splashing is not too strong

 target - substrate distance can be adjusted for minimizing the
amount of bigger clusters/droplets ejected during the ablation

 common method for ceramic (multicomponent) targets / films

 this is not a rule!

PLD geometries - conventional configuration

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 in off-center configuration of PLD the sample is moved away from the center of the target
 the main reason for using this configuration is achieving a better film uniformity (morphology)

 film uniformity is achieved only if the impingement rate depends

off-center configuration linearly on the distance to the center of the plum
with substrate rotation  for a parabolic dependence, the angle between target and substrate
surface can be adjusted - a better chance for an uniform film

PLD geometries - off-center configuration

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 in situations when splashed clusters are detrimental to the quality of the film, the center of the
plum must not be used for thin film deposition
 off-axis configuration - useful for protection against heavy clusters formed during the ablation (e.g.
during reactive ablation of multicomponent targets)
 the film is formed only by radially diffused species at the edge of the plum

 reverse face configuration - useful for extreme situations of splashing (e.g. metal targets)
 no line-of-sight deposition - reactive ablation is necessary (e.g. Zn or Ti ablation)

 shadow mask configuration - easy to obtain from conventional configuration by blocking the
center of the plume

off-axis configuration reverse face configuration shadow mask configuration

PLD geometries - center plume blocking

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 the laser incidence angle can affect the ablation process
 the energy distribution inside the laser beam is Gaussian - non-uniform irradiation
 optimum uniformity is usually achieved at 45° incidence angle - common irradiation angle
for most PLD systems
 grazing incident angles cause the laser spot to elongate on the target, resulting in loss of
fluence uniformity
 the laser fluence can affect the ablation process
 in single element targets it affects the size of the particles removed
 also depends on the reactive conditions present in the vacuum chamber - cluster
formation
 in multielement targets it affects the individual evaporation rates of the components
 congruent ablation - the fluence of the laser is so chosen that single components are
removed from the target with the same speed (rate)
 this is possible due to the very short thermal cycle during ablation (µs)
 if the heat penetration depth is smaller than the thickness of the ablated layer per each
pulse, then the stoichiometry of the plume is the same as the target
 the repetition rate of the pulsed laser has to be much higher than the rotation speed of the
target for ensuring an uniform ablation of the target surface
PLD - Laser direction and fluence
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 Stoichiometry conservation
 unlike thermal sources, the stoichiometry of the target can be reproduced in the film by
congruent ablation
 multicomponent films can be deposited from a single source
 easier as compared with co-evaporation (if you have a laser )

 Crystallinity enhancement
 ablation species are energetic particles with kinetic energy up to a few keVs and potential
energy in the form of high plasma temperature (i.e., electronic excitation)
 film crystallinity can be enhanced by using PLD - example of ZnO films (c axis orientated)
 PLD in conventional configuration - XRD investigations - (0002) FWHM is 0.21°
 the film receives the full benefit of impingement of the energetic particles in the ablation
plume
 the energy of species arriving on the substrate surface is decreased to 40-50 eV
 an energy in the range of some tens of eV is ideal for high crystalline structure
formation
 PLD in off-axis configuration - (0002) FWHM is 0.43°

PLD - Advantages
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 Reactive depositions
 the high plasma temperature of the ablation plume acts as an energy reservoir for activating
the reactive background gas (O2, O3, N2O, etc.)
 PLD is similar to magnetron sputtering but does not have the same problems in terms of
very sensitive partial pressures for the reactive gases
 the film quality is not extremely sensitive to the background gas pressure

 Multilayer growth
 due to stoichiometry preservation by PLD, only a single source is needed to grow films with
chemical complexity
 multiple-layered structures (e.g. superconductors, ferroelectric memory devices) can be
grown easily by ablating multiple sources

 Fast processing time

 PLD only needs a very small amount of target material as long as the target is larger than
the laser spot
 it is an ideal way to grow thin films of exotic materials when only a small quantity is available
 fast turnaround time when growing a thin film of a new material starting from its powder form
- PLD is the material scientist's equivalent of "rapid prototyping"

PLD - Advantages
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 Large area uniformity
 with PLD is very difficult to achieve uniform thickness films over large areas
 the ablation plume is non-Lambertian (narrow angular profile) - the cos  exponent
usually ranges between 5 and 10 but can be even higher
 the effective plume volume is rather small due to the small target/substrate distance
necessary for fully taking advantage of the laser-induced plasma in the film formation
(few cm)
 Possible solutions
 off-axis or off-center configurations combined with substrate rotation
 fast scanning of the laser spot over a higher target area for increasing the effective plume
volume
 raster movement of the substrate for achieving film uniformity over higher areas
 all these solutions are very material-oriented and cannot be presented as general

Uniform deposition front Sample uniform

by moving the target movement

PLD - Disadvantages and solutions

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 Rough surface morphology due to splashing
 micrometer-sized particles released from the target can arrive on the surface of the
substrate becoming nuclei in the film formation process or being incorporated into the film
structure at later stages
 causes of splashing:
 exfoliation - materials are removed preferentially on the
direction of the laser beam creating thin columns very instable
mechanically - thermal shock can easily break them exfoliating
the surface and creating debris which are ejected into plasma
and can travel to the substrate
 subsurface boiling - occurs if the time required to transform laser energy into heat is
shorter than the time needed to evaporate a surface layer with a thickness on the
order of absorption depth - the subsurface layer is superheated before the surface
material is completely vaporized and explodes ejecting micron-sized molten globules

 shock-wave induced droplet expulsion - occurs due to the

shock-wave recoil pressure produced during the supersonic
expansion of plasma in vacuum - the force is high enough
that small globules of molten material are expulsed from the
surface
PLD - Disadvantages and solutions
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 Target surface conditioning
 simple way of reducing target exfoliation by constant mechanical treatment (polishing) or by
a first step of target irradiation using low laser fluencies
 Particle filter
 uses the fact that splashed particles have much lower speeds than atomic
and molecular species and can be therefore mechanically removed
 avoid the splashed particles from reaching the substrate rather than avoid
splashing by using rotating vanes, mechanical shutters, etc.

 Special target - substrate geometry

 cross plume configuration - a gas plume is
formed which interact with the laser plume for
avoiding big particles to reach the substrate
 the collisional frequency inside the intersecting zone is high -
scattered atomic and molecular species will be deviated toward
the substrate, while micron-sized particles from splashing will
continue their trajectories due to their heavy mass
 ablation plasma is increased when using a reactive gas

PLD - solutions to avoid splashing

P.R. Willmott, Prog. Surf. Sci. 76 (2004) 163 14
PLD - solutions to avoid splashing
P.R. Willmott, Prog. Surf. Sci. 76 (2004) 163 15
 Special target - substrate geometry
 crossed-beam configuration - a second
laser beam is used on a second target
 the splashing droplets produced on the
surface of each target will preferentially
move on the corresponding beam direction
 a diaphragm placed at the beam crossing
point will mechanically filter the big particles
 the droplets that escape through the
diaphragm continue their linear motion,
while both plumes formed due to ablation
will interact changing their directions due to
atomic / molecular collisions
 Liquid targets
 liquid targets can be used for minimizing the ablation
splashing - the energy associated to the recoil
pressure is dissipated in the ripples on the liquid
surface - only a minimum force will still be present at
the edge of the liquid target
PLD - solutions to avoid splashing
P.R. Willmott, Prog. Surf. Sci. 76 (2004) 163 16
 Aurora PLD
 the degree of ionization in the ablation plume of PLD
can be increased by introducing a strong magnetic field

 the strongest effect occurs when the magnetic field lines

cross the expanding plasma at right angles, producing the
largest Lorentz force
 the electrons spiral around the magnetic field lines and
are confined in the plasma much more effectively than if
the magnetic field was absent
 ions (X+) can also be significantly shifted by the
magnetic field
 a mask in front of the substrate will protect the substrate
from droplets, while the ionic species can be deflected
again towards the substrate (if the polarity of the magnet
is correctly chosen)

 the biggest enhancement of ionization is achieved when the magnet is placed very close to
the substrate - magnetic/magnetizable films ???

PLD enhancement - Aurora PLD

P.R. Willmott, Prog. Surf. Sci. 76 (2004) 163 17
Pulsed Laser Deposition
Materials survey
 Metals
 PLD does not present any absolute advantage for metal deposition
 is preferred only in situations when stoichiometry is critical:
 e.g. cathode fabrication for photo-emission devices (Pb, Mg, Y)
 for the same incident laser photon energy, metals with lower work function
have higher Quantum Efficiency (percentage of incident photons that produce
electron-hole pairs)
 multilayer films are easily achieved

 relevant for magnetic and non-equilibrium

alloys (e.g. Co-Pt)

PLD Materials
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 Semiconductors CdS/ITO

 PLD has a major drawback for III-V semiconductor thin films:

splashing
 II-VI semiconductor (Chalcogenides) thin films are very
successful with PLD
 CdTe, ZnS, ZnSe, etc. - lack a liquid state - do not splash
 CdS/CdSe solar cell applications CdTe/ITO

 photoluminescence properties of CdSxTe1-x

 Single cation oxides

 tough competition with e-beam and sputtering
 successfully established with better properties for epitaxy of CdTe/CdS/ITO
various oxides
 yttria-stablized zirconia (YSZ) on Si
 epitaxy of MgO on GaAs

PLD Materials
A. Bylica et al., Thin Solid Films 511 (2006) 439 20
 Diamond-like Carbon (DLC)
 Carbon films with high values of density, hardness, electrical resistivity, chemical
inertness, IR transparency, and the lack of detectable long range structural order
 the qualities of thermal conductivity, microhardness and field emission efficiency are
much improved using PLD

 Nitrides
 growth of CNx with highest N content can be done by PLD
PLD Materials
A.A. Voevodin,et al., Surf. Coat. Tech. 82 (1996) 199 21
 Perovskites
 ABO3 - cubic, orthorombic or tetragonal structure
B
 the main “player” for ferroelectrics - YBCO, PZT, etc. A

 stoichiometric films with high cristallinity  - only small surface 

O2-
 Pb(Zr, Ti)O3 ferro/piezoelectric films
 good cristallinity
 low fatigue

 Organic materials
 must involve a nonthermal process to avoid dissociation - UV PLD is a logical candidate
 the ablation mechanism is mainly photolytic, involving "zipping" polymer chains into small
units and repolymerizing them on the substrate
 polyethylene (PE), polycarbonate (PC), polyimide (PI), polymethylmethacrylate (PMMA),
polyphenylene sulfide, Cu-phthalocyanin
PLD Materials
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