Types of Reactors

1. Cold walled reactors

2. Hot walled reactors
1. Cold Walled Reactors
 The walls of the reactor are cold and usually no
deposition occurs on them.
 Risk of contamination from vapor/wall reactions is reduced.
 The homogeneous reactions are suppressed and the importance of surface
reactions is increased.
 As a result of a steep temperature gradient,
Introducing severe natural convection, uniformity with respect to microstructure
and thickness may be difficult to control.
 Advantages

 A cold-wall reactor has the

advantage of:
1. Flexibility
2. High cleanliness
3. High cooling rates
4. Easy construction of automated
substrate handling systems.
 Hot Walled Reactor
 In the hot-wall system , the reactor is surrounded by the furnace and the
substrates and reactor walls are at the same temperature.
 This means that the deposition not only takes place on the substrate but also on
the inside of the reactor walls.
 With thicker films on the reactor walls there is a risk that particles will become
detached (spall) from the walls and fall down during the deposition resulting in
pin-holes in the coating.
 Another source of contamination may be due to reactions between the hot
reactor walls and the process gases.
 These reactions may yield gaseous reaction products, which then carry the wall
material to the substrate where a re-deposition of the wall material may occur.
 Upon transporting the reaction gas mixture through a hot-wall reactor there is a
successive depletion with respect to the reactants.
 Such a depletion yields different deposition conditions within the reactor.
 Hot Walled Reactor (cont..)
 For compensation of the depletion and for achievement of acceptable
deposition conditions throughout the reactor, different techniques can be
used:
 Introduction of fresh reaction gas at different positions in the reactor.
 Arrangement of a longitudinal temperature gradient in the reactor to increase
the yield of the process.
 Use of geometrical restrictions in the reactor to increase the linear gas flow
velocity
 The addition of species to the reaction gas to reduce the deposition rate,
particularly at the entrance of the reactor.
 In TiC CVD, for instance, from TiCl4, CH4 and H2, HCl is added in order to get an
acceptable uniform coating thickness in the longitudinal direction of the
reactor.
 The hot wall reactor must necessarily be employed in processes where
homogeneous reactions are important.
 It also has a high throughput, which means that many (i.e. thousands of)
substrates can be deposited simultaneously.
 Physical vapour deposition methods
• Coatings produced by physical vapour
deposition (PVD) in which the coating vapour
flux is created by a physical process such as
evaporation or sputtering from a solid target
have been available since the technology
necessary to sustain the required vacuum was
developed.
• The development of diffusion pumps in the
1920s made it possible to evacuate a
deposition chamber to a low enough pressure
for controlled vacuum evaporation.
• Although evaporated metal coatings have
been used in some tribological applications,
such as to lubricate threads on fasteners for
the automobile industry, it has been the
development of more advanced PVD
processes enabling compound and ceramic
coatings to be deposited with a high density
which has revolutionised the PVD wear-
resistant coatings market.
 Fundamentals of physical vapour
deposition
• The PVD coating process involves deposition of the
coating on an atom by-atom basis from the vapour
phase.
• There are four important stages to this.
1. Production of the vapour flux by a physical
process (evaporation or sputtering).
2. Transfer of the coating atoms from target to
components through the gas phase.
3. Deposition of the coating elements on the
component surface.
4. Incorporation of coating atoms into the layer.
E-beam Evaporation
 Evaporation
• The easiest way to convert a solid material into a vapour
flux is by evaporation. If the target material is heated, its
vapour pressure will increase and at a critical temperature
will exceed the ambient pressure and vapour
will stream away from the target.
• Figure shows the typical variation in vapour pressure with
increasing temperature for a range of chemical elements.
• The vapour pressure increases with increasing temperature
for all elements but there is a considerable variation in
vapour pressure between different elements related to
their melting temperature.
• In order to develop a reasonable coating flux without an
extreme heat input into the target it is usual to carry out
the process under vacuum (typically 10−5 to 10−6 torr).
• A number of methods of heating have been
developed for evaporation systems including
resistive heating, electron beam heating, arc
heating and plasma heating.
• In some commercial coating systems the solid
metal to be evaporated is held in a water-
cooled crucible to prevent contamination of the
target and the heating is localised to the target
region only In other systems a crucible or
resistance heating support structure is used
which does not chemically react with the
material to be evaporated (e.g. TiB2 boats for
aluminium).
• Metal coating rates produced by evaporation
can be up to hundreds of micrometres per
minute in some cases which makes the
technique competitive with many other
deposition technologies.
• However, rates are much reduced if
compounds are evaporated.
 Sputtering
• In the sputtering process the target is bombarded
by heavy ions such as argon, and target atoms are
ejected into the gas phase owing to the
momentum transfer from the bombarding
species.
• The ion bombardment can be created by the
interaction of a plasma or ion beam with the
target surface, both of which require operation in
vacuum. Typically cathode sputtering takes place
in an inert gas at a pressure of 10−2 to 10−1 torr
and an applied potential of 500–1000 V.
• Sputtered atoms are ejected with a range of
energies that are related to the energy of the
bombarding ion.
• For typical process conditions the mean energy
of the sputtered atoms is around 10 eV. Only
about 1% of the sputtered species is charged.
• Simple sputtering methods suffer from two
main drawbacks when compared with
conventional evaporation:
• low coating rates and
• a high thermal load of the substrates due to
bombardment by secondary electrons.
• By using a magnetron source it is possible to
confine the electrons close to the cathode
surface by means of a magnetic field,
increasing the plasma density and reducing
the electron heating of the substrates.
 Vapour transport
• In an ideal system, once the coating flux has been
produced, it streams out into the vacuum chamber and
travels in a straight line until it encounters the
components, the chamber walls or the sample supports
where it condenses to form a deposit.
• In practical systems the ambient pressure is not always
low enough for this to happen and the mean free path
between collisions with the residual gas in the system is
less than the distance between target and samples.
• Some gas scattering will therefore occur. Indeed, close
to the targets where the coating flux originates, the
local pressure will be higher and gas scattering between
coating atoms is likely to occur.
• In some systems the coating flux passes through a
region of plasma where some of it becomes
ionised.
• The plasma is generated either by the coating
process itself (e.g. in sputtering) or by auxiliary
electrodes which are independent of it.
• This can help to densify the coating and to
improve its properties
• The proportion of the flux which is ionised by this
method is usually very low (about 1%).
 Coating deposition
• When the coating flux encounters the components (or
the chamber walls) it will condense and form the
coating layer.
• A single coating atom will land somewhere on the
substrate and then can move a short distance until it
finds a site where it can become incorporated in the
coating.
• The mobility of such an adatom depends on the
substrate temperature and the energy of the arriving
coating atom.
• For low-energy adatoms, such as those produced by
evaporation, the mobility is low and the atom remains
close to where it was first deposited.
 Reactive deposition processes
• Reactive gases may also be added to the chamber
in order to maintain the stoichiometry of
compound coatings or to form compound
coatings from metallic targets.
• Since the evaporation or sputtering rate of
compounds is much less than that of the metallic
elements that they contain, this is a way of
increasing the coating rate, but the process
control must be very precise to take advantage of
this.
• Direct evaporation is usually considered
effective and reliable for metals but for ceramic
materials is difficult because of their high
melting points, low vapour pressure and
tendency to dissociate.
• Therefore reactive methods are best employed
to obtain stoichiometric coatings of carbides,
nitrides or oxides, the metal being evaporated
in the presence of an appropriate gas such as
methane, nitrogen or oxygen
• Activated reactive evaporation (ARE) operates at a
pressure in the range 10−4 to 10−3 torr when a glow
discharge is initiated by the incorporation of an
anode in the coating chamber which ionises and
increases the reactivity of the gas species.
• Figure shows the variation in coating rate with the
mass flow of the reactive gas into a sputtering
chamber. It is clear that, on increasing the amount
of reactive gas supplied to the system, the coating
rate is reduced once a certain gas flow is achieved
and drops to a lower plateau value at high gas flow.
• This represents the change from the coating
rate of the pure metal to the coating rate of
the compound.
• On reducing the reactive gas flow the change
back to the metal coating rate occurs at a
lower gas flow than on increasing and a
noticeable hysteresis is produced.
• Control of the process by gas flow alone is
therefore very difficult.
• The reason for this behaviour is associated with
what happens to the gas when it enters the
chamber.
• The gas that is introduced can end up reacting
with the deposited atoms to make the coating as
required but some of it will react with the surface of
the target to form a compound layer if the partial
pressure of the gas in the chamber is high enough.
• This process is called target poisoning. If such a
compound layer forms on the target, the sputtering
yield drops and the coating rate is reduced.
• Reducing the partial pressure of reactive gas
after this may not have an immediate effect as
the compound layer needs to be sputtered
from the target before metal behavior is re-
established.
• The amount of reactive gas required is
therefore just enough to enable the desired
coating to be produced, but in doing so it must
• be accepted that some target poisoning will
occur and this must be limited if the highest
coating rates are to be achieved.
• In order to reduce the effect of target
poisoning most commercial sputtering
systems use some sort of partial pressure
control based on analysis of the plasma
in front of the target by atomic emission
spectroscopy
 Deposition of alloy, compound and
multilayer coatings
• Compounds and alloys may be evaporated as well
as elements but in general the composition of the
coating is not the same as the source material
• because the vapour pressures of the different
constituents are not the same and compound
targets may dissociate on evaporation.
• In many cases, source alloys of one well-defined
composition are developed which produce an
alloy of a different desired composition when
evaporated
• If the alloy contains elements with widely different
vapour pressures, such as NiAl, this may be very
diffi cult to achieve and the difficulty increases as
more alloying elements are added.
• For this reason, evaporation is generally only used
for simple alloys and compounds.
• The stoichiometry of compound coatings is often
maintained by backfilling the chamber with a
controlled partial pressure of an appropriate gas;
for instance oxygen backfills are necessary to
• maintain the stoichiometry of evaporated oxide
coatings
• Producing conducting coatings such as metals
or some transition-metal nitrides by
sputtering is relatively straightforward by
reactive sputtering from metallic targets.
However, the quality of the target is very
important to achieve this.
• One advantage of the sputtering process for
producing alloy or complex compounds is the
fact that the sputtered atoms become
intimately mixed in the gas phase and it is not
necessary to have a target with the exact
composition of the intended coating.
• Rather a compound target may be made with
areas of different material added as inserts, or
a powder target produced by mixing and
pressing powders to achieve the correct
average composition.
• After sputtering, the coating has a uniform
composition which is close to that of the average
target composition since sputtering yields do not
vary much for different elements. This approach
can be used to determine very rapidly the correct
target composition required to deliver a specified
coating.
• For this reason, more complex alloys and
compound coatingsare generally deposited by
sputtering.
 Future trends
• PVD coating technologies have matured since they were
fi rst introduced and are now well-established
commercial processes. The cost of vacuum engineering
and power supplies has also fallen in the period and so
the economic disadvantages which the technology
suffered in its early history are much less apparent.
• The drop in running costs and the increase in system
reliability have meant that PVD coatings are increasingly
competitive in the marketplace and the number of
applications continues to grow.
• One area of current interest is the use of PVD coatings
to replace similar electroplated coatings on the grounds
that the environmental damage from the PVD process is
significantly less.
• The range of PVD coatings in use and the range of
applications in which they offer benefits will also
expand.
• This will partly be driven by improvements in the
deposition technologies which produce them, by
the characterisation techniques used for
assessing the coatings and by the emergence of
better rules for incorporating the coatings as an
integral part of the component design process
 Arc Vapor Deposition
• Arc vapor deposition is a PVD technique which
uses the vaporization from an electrode under
arcing conditions as a source of vaporized
material.
• Arcing conditions consist of a high-current low-
voltage electrical current passing through a gas or
a vapor of the electrode material.
• The arc voltage only has to be near the ionization
potential of the gas or vapor (>25 volts).
• An electric arc is an electrical breakdown of a gas
which produces a ongoing plasma discharge,
resulting from a current through normally
nonconductive media such as air.
• The arc occurs in the gas-filled space between two
conductive electrodes (often made of tungsten or
carbon) and it results in a very high temperature,
capable of melting or vaporizing most materials. An
electric arc is a continuous discharge, while a
similar electric spark discharge is momentary.
• An electric arc may occur either in Direct
current circuits or in alternating current circuits. In
the latter case, the arc may re-strike on each half
cycle of the current.
 Plasma
• is a state of matter similar to gas in which a
certain portion of the particles is ionized.
• Heating a gas may ionize its molecules or atoms
(reduce or increase the number of electrons in
them), thus turning it into a plasma, which
contains charged particles: positive ions and
negative electrons or ions.
• Ionization can be induced by other means, such
as strong electromagnetic field applied with
a laser or microwave generator
• Most of the ejected material is thermally
evaporated but some is ejected as molten
droplets or solid particles from the cathode.
• A high percentage of the vaporized atoms are
ionized in the arc vaporization process.
• The arc can be established between closely
spaced electrodes in a good vacuum (vacuum arc)
by vaporizing some of the electrode material, or
between electrodes in a low pressure or high-
pressure gaseous environment (gaseous arc)
• In PVD processing, arc vaporization can be
considered a unique vaporization source along
with thermal vaporization and sputtering.
• Arc vaporization was first reported by Robert
Hare in 1839 and has been of concern in arc
melting of alloys.
• Early use of vacuum arc deposition of thin film
was to deposit carbon[10] and metal[11] films.
• Arc deposited carbon has long been used as a
replication film in electron microscopy.
• Arc vaporization in a low pressure vacuum
occurs when a high current-density, low
voltage electric current passes between
slightly separated electrodes in a vacuum,
vaporizing the electrode surfaces and forming
a plasma of the vaporized material between
the electrodes as shown in the Fig.
• In order to initiate the arc, usually the electrodes
are touched then separated by a small distance.
On the cathode a “cathode spot” is formed that
has a current density of 104–106 A/cm2.
• This current density causes arc erosion by melting
and vaporization and by the ejection of molten
• or solid particles.
• On the anode the current density is much less but
can be sufficient to melt and evaporate the anode.
• A high percentage of the vaporized material is
ionized in the arc and the ions are often multiply
charged
 Gaseous Arcs
• The gaseous arc involves utilizing a gaseous
environment ranging from a few mTorr to
atmospheric pressure or even higher.
• When using a gaseous arc for film deposition, the
gas pressure is kept low to prevent gas phase
nucleation of the vaporized material and allow the
acceleration of ions from the plasma without
collision.
• In the gaseous arc, gaseous atoms as well as atoms
from the electrodes are ionized and sustain the
discharge. This allows the arcing electrodes to be
more widely separated than in the vacuum arc.
• The gas that is used in gaseous arc deposition
can be an inert gas such as argon if the
deposition of an elemental material is desired
or can be a reactive gas or a mixture of
reactive and inert gas if the deposition of a
compound material (reactive deposition) is
desired.
 Anodic Arcs
• In an arc discharge, if the anode is molten,
material evaporates from the molten anode
surface into the arc and the source is called an
anodic arc source.
• This type of arc is sometimes called a distributed
arc since the current density is much lower on the
anode than in the cathode spot (~10 A/cm2 vs
104–106 A/cm2).
• The anodic arc has the advantage that molten
globules are not formed.
• Since the anode is molten there will be
preferential vaporization of constituents of an
alloy electrode so deposition of alloy materials
and multi-component compound materials can
be difficult using the anodic arc.
• The degree of ionization of the vaporized
electrode material in the anodic arc is generally
less than in the cathodic arc and the ions are
typically singly charged.
• An example of using the anodic arc is the
deposition of adherent silver films on beryllium
using a hot hollow cathode electron source
with magnetic beam-bending as shown in Fig.
• By applying a high negative DC bias on the
beryllium substrate, the beryllium is sputter-
cleaned by the silver and gaseous ions then by
reducing the bias, an adherent silver film is
formed.
 Cathodic Arcs
• If the vaporization primarily occurs from the cathode
surface by arc erosion the system is called a continuous
cathodic arc source.
• The cathode can be molten or solid with a water cooled
solid cathode (“cold cathode”).
• The cold cathode source is the most common cathodic
arc source for film deposition. In order for a stable arc to
form there must be a minimum current passing through
the arc.
• Minimum arc currents vary from about 50–10A for low
melting point materials such as copper and titanium to
300–400A for refractory materials such as tungsten.
• Most of the arc voltage drop will occur near the cathode
surface.
• The arc voltage can be from about 15 volts to
100 volts depending on the ease of electron
• motion from the cathode to the anode (i.e.,
cathode design).
• The energy dissipation in the arc is about (very
approximate):
• Problems with the cathodic arc deposition
technique include stabilization and movement of
the arc on the solid surface and the formation of
molten micron-sized “globules” (or “macros”) of
the ejected material from the solid surface.
Macros are not formed if the cathode is molten.
• If the arc is allowed to move randomly over the
surface the arc source is called a random arc
source. If the arc is confined and caused to move
over the surface in a particular path the source is
called a “steered arc” source.
• There are a number of different steered arc
source designs using magnetic fields to steer the
arc.
• Steered arc sources generally produce fewer
macros than random arc sources.
• The high-density electron current on the
solid arc-cathode forms a cathode spot
which generally moves over the surface
until it is extinguished.
• The electron current in the spot is from
30–300 amps and the current density in
the spot can be greater than 104 A/cm2.
• If the current density is very high, the arc
will break up into two or more spots
(arcs).
• Arc movement on the cathode is affected by
the gas composition and pressure, cathode
material and impurities and the presence of
magnetic fields.
• When there is no magnetic field, the arc tends
to move in a completely random manner. If
the cathode is a disk, then statistically the arc
is mostly in the center and the erosion will
mostly be in the center of the disk.
 Macros
• Macros are formed by ablation of molten or solid
particles by thermal shock and hydrodynamic
effects in the molten spot on a solid surface.
Macros are not formed from molten anodic or
cathodic surfaces.
• The number and size of macros produced from
the solid arc cathode surface depends on the
melting point and vapor pressure of the cathode
material and the arc movement.
• Large (tens of microns diameter) macros are
formed with low melting point materials and slow
arc movement while small macros (< 1 micron)
are formed with high melting point materials and
rapid arc movement.
• For example, in arc deposition of ZrN from a
zirconium cathode, it is estimated that 1% of the
deposited zirconium is in the form of globules.
• The globules have a velocity of 250–350 m/sec.
Material may thermally evaporate from the
• ejected molten globules and many of the neutral
atoms found in arc vaporization are thought to be
produced by thermal evaporation from the ejected
globules.
• This effect can cause the composition.
• The globules can be “filtered” from the arc using
various means such as the “plasma duct”.
• The number and size of the globules increases
with lower melting point materials, high cathode
currents, and high cathode temperatures.
• The number of macros that deposit on the
substrate can be minimized by decreasing the arc
current, increasing the source-substrate distance,
increasing gas pressure.
 Cathodic Arc Sources
• There have been a number of designs of
cathodic arc sources.
• Each source has to have some way of initiating
the arc and a configuration that re-ignites the
arc when it is extinguished.
 Arc Initiation
• The arc can be initiated by touching and
separating the electrodes, using a high voltage
“trigger arc,” laser ionization or some other
technique that forms ions and electrons in a path
between the electrodes.
• Typically a trigger arc is obtained from a high
voltage on an auxiliary electrode near the
cathode surface causing the arc to form.
• When an arc is extinguished, the inductance in
the arc power supply gives a voltage spike which
reignites the arc.
• The original patent on the non-magnetic cathodic
random arc source was by Sablev.
• Random arc sources are generally round and
either surrounded by a shield separated from the
target or an insulator in contact with the target
(passive arc confinement) as shown in Fig.
• As the arc enters the space between the target
and the shield or moves onto the surface of the
insulator, it is extinguished.
• The anode can be either the chamber walls or a
separate surface in the vacuum system.
 Steered Arc Sources
• In the steered arc source the arc is confined to
the surface by a magnetic field and caused to
move in a specific path and with a greater
velocity than with the random arc.
• Usually the magnetic field has an arched
configuration that closes on itself as shown in Fig.
• The magnetic field can be established using
elecromagnets or permanent magnets.
• Permanent magnets can be physically moved to
steer the arc.
 Pulsed Arc Sources
• Pulsed arcs can be made by making and
breaking the arc circuit by repetitively
touching the arcing surfaces or by using a
pulsed DC power supply.
• Pulsing is usually done in vacuum and usually
does not require active cooling.
• This is the type of source that is used in some
metal ion sources.
• Pulsed cathodic arc plasma sources are
characterized by currents up to 5000 A, pulse
length of few milliseconds to
few nanoseconds and relatively high
repetition rates (from few Hz to few kHz).
• A major advantage of pulsed operation is the
relatively low average power which reduces
the cooling requirements.
 Filtered Arcs
• The macros can be removed from the arc
plasma (“filtered”) by several techniques.
• The most common technique is the use of a
plasma duct in the form of a bent “knee”
configuration.
• The macros are deposited on the walls and
only charged film-ions get to the substrate.
• Typically, the deposition rate is cut by about
one-half when using the plasma duct.
 Anodic Arc Sources
• Anodic arc sources are basically evaporation
sources heated by low-voltage high-current
unfocused electron beams.
• The electron beam can be bent by a magnetic
field so that the emission source is out-of-line-
of-sight of the evaporation source as shown in
Fig. it can be in the line-of-sight.
 REACTIVE ARC DEPOSITION
• In reactive arc deposition, the reactive gas is
activated in the arc plasma.
• Usually the deposition is done in an ion plating
mode, i.e., ions of both the film material and the
reactive gas are accelerated to the substrate.
• A partial pressure of inert gas may be needed to
help sustain the arc if the composition of the
deposited film is graded by controlling the
availability of the reactive gas
 ARC MATERIALS
• Cathodes for cathodic arcing should be made
from fully dense material.
• Pressed powder targets should be avoided
since they do not give stable arcing and
particles are ejected from the arcing surface.
• The molten material for anodic arcing is usually
contained in a crucible in much the same way
as for thermal evaporation
 ARC VAPOR DEPOSITION SYSTEM
• Arc vapor deposition does not have any
special vacuum requirements.
• In reactive arc deposition, gas flow control
must be established and controlled.
• In the cathodic arc deposition from a cooled
cathode, coolant flow and temperature
sensors should be used in the cathode coolant
circuit.
• Usually in arc vapor deposition, the deposition
chambers are large to allow the fixtures to be
placed well away from the arc source.
• This is similar to the vacuum deposition chamber
shown in Fig.
• When using a cathodic arc deposition, often
several sources are positioned in the chamber.
• Another cathodic arc configuration uses a
centrally positioned post as the cathodic
electrode.
• When using such a large chamber, it means that
large areas will collect excess deposited film and
have to be cleaned.
 Power Supplies
• Arcing uses low-voltage (100 volts) high-current
(hundreds of amperes) power supplies much like
arc-welding power supplies.
• The power supply must have a high inductance in
order to form the high voltage pulse necessary to
re-ignite an arc when an arc is quenched.
• In addition to the arc supply, a high voltage (to
1000 volts) DC bias power supply is often needed
 Fixtures
• Arc vapor deposition often involves coating three-
dimensional objects and rotatable fixtures are necessary
that allow deposition over the whole surface with a
uniform angle-of-incidence of the depositing vapor flux.
• Often the fixture is biased to some voltage to allow
sputter cleaning and energetic bombardment of the
growing film.
• In some designs, the arc sources are mounted on the
chamber walls and in other designs the arc source is a
post in the center of the chamber.
• The positioning of the arc source(s) affects the design of
the fixtures and tooling used to hold and move the
substrates
 PROCESS MONITORING AND
CONTROL
• The amount of deposited film is determined by
the process parameters, fixture configuration and
deposition time.
• Often the substrates to be coated are heated in
the deposition system. For example, tool bits are
heated to 300–400oC.
• This can be donewith radiant heaters or by ion
bombardment during sputter cleaning.
• The temperature is monitored using a maximum-
reading infrared optical pyrometer.
 CONTAMINATION DUE TO ARC
VAPORIZATION
• The most common contaminants are
particulates generated during cathodic arc
deposition.
• These can be molten globules when ejected
• from the cathode or they may be solid
particles such as those ejected from carbon or
pressed powder targets.
 ADVANTAGES AND DISADVANTAGES
OF ARC VAPOR DEPOSITION
• Arc vaporization provides a higher vaporization
rate than does sputtering but not as high as can
be obtained by thermal evaporation.
• Vaporization from solid surfaces allows cathodic
arc sources to be mounted in any configuration.
• The low voltage power supplies used are
attractive from a safety standpoint.
• Disadvantages
• The production of macros can be a determining
factor in some applications.
 Physical Sputtering and
Sputter Deposition
• The physical sputtering (sputtering) process,
or pulvérisation in French, involves the
physical (not thermal) vaporization of atoms
from a surface by momentum transfer from
bombarding energetic atomic sized particles.
• The energetic particles are usually ions of a
gaseous material accelerated in an electric
field
• The terms “chemical sputtering” and
“electrochemical sputtering” have been
associated with the process whereby
bombardment of the target surface with a
reactive species produces a volatile species.
• This process is now often termed “reactive
plasma etching” or “reactive ion etching”
and is important in the patterning of thin
films.
• Sputter deposition, which is often called just
sputtering, is the deposition of particles
whose origin is from a surface (target) being
sputtered.
• Typically the use of the term sputter deposition
only indicates that a surface being sputtered is
the source of the deposited material.
• In some cases, the sputtering configuration may
be indicated (e.g., ion beam sputtering,
magnetron sputtering, unbalanced magnetron
sputtering, RF sputtering, etc.).
• In some cases special sputtering conditions may
be indicated such as reactive sputter deposition
for the deposition of compound films or bias
sputtering, when a bias is placed on the
substrate so that there is concurrent ion
bombardment of the depositing film
 Sputter deposition can be done in:
• A good vacuum (< 10-5 Torr) using ion beams
• A low pressure gas environment where sputtered
particles are transported from the target to the
substrate without gas phase collisions (i.e.,
pressure less than about 5 mTorr) using a plasma as
the ion source of ions
• A higher pressure gas where gas phase collisions
and “thermalization” of the ejected particles occurs
but the pressure is low enough that gas phase
nucleation is not important (i.e., pressure greater
than about 5 mTorr but less than about 50 mTorr).
 Thermalization

• Energetic molecules moving through a gas

lose energy by collisions with the ambient gas
molecules, scatter from their original
direction, and become thermalized
• Sputter deposition can be used to deposit films
of compound materials either by sputtering
from a compound target or by sputtering from
an elemental target in a partial pressure of a
reactive gas (i.e., “reactive sputter
deposition”).
• In most cases, sputter deposition of a
compound material from a compound target
results in a loss of some of the more volatile
material (e.g., oxygen from SiO2) and this loss
is often made up by deposition in an ambient
containing a partial pressure of the reactive
gas and this process is called “quasi-reactive
sputter deposition.”
 PHYSICAL SPUTTERING
The sputtering yield (ratio of atoms sputtered to the
number of high energy incident particles) depends on
1. the mass of the bombarding particle as well as its
energy.
2. The sputtering yield is sensitive to the angle-of-
incidence of the bombarding particle.
3. There is a “threshold energy” below which
sputtering does not occur no matter how high the
bombarding flux.
4. Many sputtered atoms have kinetic energies much
higher that than those of thermally evaporated atoms.
5. Atoms ejected from single crystals tend to be ejected
along directions of the close packed planes in the crystal.
6. In a polycrystalline material some crystallographic
planes are sputtered faster than are others (preferential
sputter etching).
7. Atoms sputtered from an alloy surface are deposited
in the ratio of the bulk composition not their relative
vapor pressures as is the case in thermal vaporization.
8. Sputtering yields decrease at very high energies
because the ions lose much of their energy far below the
surface.
9. The sputtering yield is rather insensitive to the
temperature of the sputtering target.
• Effects 1 through 7 above are important to the
growth of films by sputter deposition. This is
particularly true for low-pressure (<5 mTorr)
sputtering where the energetic sputtered
atoms and reflected high energy neutrals are
not “thermalized” by collision between the
sputtering source (target) and the substrate.
• Figure shows the processes that occur at the
surface region and in the near-surface region of
the bombarded surface.
• The bombarding particles can physically penetrate
into the surface region while the collision effects
can be felt into the near-surface region.
• The bombarding particle creates a collision
cascade and some of the momentum is
transferred to surface atoms which can be ejected
(sputtered).
• Most of the transferred energy (>95%) appears as
heat in the surface region and near surface region.
• Some of the bombarding particles are reflected as
high energy neutrals and some are implanted into
the surface.
• When sputtering is performed in a low pressure or
vacuum environment, high energy reflected neutrals of
the bombarding gas and high energy sputtered atoms
from the target bombard the growing film and affect
the film formation process.
• In sputtering, the sputtering target generally is actively
cooled.
• The cold surface minimizes the amount of radiant heat
in a sputtering system and is an advantage over thermal
evaporation in vacuum where the radiant heat load can
be appreciable.
• The low level of radiant heat is one factor that allows
thermally-sensitive surfaces to be placed near the
sputtering target.
• Cooling also prevents diffusion in the target which
could lead to changes in the elemental composition in
the surface region when alloy targets are used.
• The mass of the bombarding species is
important to the energy and momentum
transferred to the film atom during the
collision.
• From the Laws of Conservation of Energy and
the Conservation of Momentum the
• energy, Et, transferred by the physical collision
between hard spheres is given by

where E = energy, M = mass, i = incident particle, t = target particle and θ

is the angle of incidence as measured from a line joining their centers of
masses
• The maximum energy is transferred when cosθ
= 1 ( zero degrees) and Mi = Mt. Therefore
matching the atomic mass of the bombarding
ion to the target atom is important to the
sputtering yield.
• This makes krypton (84 amu), xenon (131 amu)
and mercury (201 amu) ions attractive for
• sputtering heavy elements, and light ions such
as nitrogen (14 amu) unattractive.
• This advantage is typically outweighed by other
considerations such as cost of the sputtering
gas, health concerns.
• Typically argon (40 amu) is used for inert gas
sputtering since it is a relatively inexpensive
inert gas.
• Mixtures of argon and nitrogen, argon and
oxygen or argon and methane/acetylene are
used for sputtering in reactive sputter
deposition.
 Sputtering Yields
• The sputtering yield is the ratio of the number
of atoms ejected to the number of incident
bombarding particles and depends on the
chemical bonding of the target atoms and the
energy transferred by collision.
• The sputtering yields of various materials
bombarded by a variety of ion masses and
energies have been determined
experimentally
• Note that the sputtering yields are generally
less than one at bombarding energies of
several hundred electron volts, indicating
• the large amount of energy input necessary to
eject one atom.
• Sputtering is much less energy efficient than
thermal vaporization and the vaporization
• rates are much lower than can be attained by
thermal vaporization
• The preferential sputtering of different crystallographic
planes in a polycrystalline sputtering target is used for
sputter etching in metallographic sample preparation
and can lead to roughening of the target surface with
use.
• The roughening and feature-formation can lead to the
decrease of the sputtering yield of the target surface as
it goes from a smooth to a rough morphology.
• Roughening and preferential sputtering, along with
stress from fabrication, can also lead to particulate
generation from the target for some target materials.
 Sputtering of Alloys and Mixtures
• Since sputtering is generally done from a solid
surface ideally, if there is no diffusion, each layer
of atoms must be removed from the surface
before the next layer is subject to sputtering as
shown in Fig.
• This means that the flux of sputtered atoms has
the same composition as the bulk composition of
the sputtering target although, at any instant, the
• surface layer of the target will be enriched with
the material having the lower sputtering yield.
• In some cases where the mixture is of materials
having significantly different masses or sputtering
yields, the sputtered composition may be
different than the target composition.
• For example, carbon on a copper surface will
form islands which have a low sputtering yield,
and tungsten atoms on an aluminum surface will
move around on the surface rather than sputter.
 Sputter Processing
• The simplest type of
sputtering apparatus, the
DC diode, consists of two
plates, a vacuum chamber,
and a power supply
(see Figure).
• A sputtering gas, typically
argon, is introduced at a
pressure in the millitorr
range, and voltage is
applied across the plates.
• Above a threshold breakdown voltage
(depending on sputter gas, pressure, and
cathode material), a plasma discharge forms
in which positively charged ionized gas atoms
are drawn to the negatively charged cathode.
• An important process that takes place in a glow
discharge is sputtering, which can occur if the
voltage applied to the cathode is sufficiently high.
• When the ions and fast neutrals from the plasma
bombard the cathode target, they not only
release secondary electrons, but also atoms of
the cathode material, referred to as sputtering.
• When species are sputtered off a cathode target
and subsequently used as film forming material,
the process belongs to what is referred to as a
physical vapor deposition
• Sputtering is most easily performed by
exposing a cathode target to a gas discharge:
either a dc discharge or a magnetron
sputtering discharge, whereas ion beam
sputter deposition is also a well-established
PVD technique.
• Other PVD techniques include evaporation,
pulsed laser deposition, cathodic arc
deposition, and ion plating.
 DC glow discharge
• The term gas discharge refers to a flow of electric
current through a gaseous medium. For a current
to flow, some of the gas atoms and molecules
have to be ionized.
• Furthermore, this current, the discharge current,
has to be driven by an electric field.
• The discharge current, which provides power to
the discharge, has to be continuous throughout
the length of the discharge.
• There is a transition in the discharge with regards
to which charged species carries the discharge
current.
• Let us assume two parallel electrodes separated
by a distance L and with applied potential VD.
The gap between the electrodes is filled with gas
at pressure p, the working gas pressure.
• The type of discharge that is formed between the
two electrodes depends upon the pressure of the
working gas, the nature of the working gas, the
applied voltage, and the geometry of the
discharge.
• When a voltage is first applied, the discharge current
is very small. This current consists of contributions
from various external sources such as cosmic
radiation generating free electrons and ions.
• When the voltage has become large enough to collect
all these charged particles, this current remains
nearly constant with increased voltage.
• As the voltage is further increased, the charged
particles eventually achieve enough energy to
produce more charged particles through collisions
with the working gas atoms or by bombardment of
the electrodes leading to generation of secondary
electrons.
• Once breakdown has occurred, the discharge
becomes self-sustaining and takes the form of
a glow, and the gas becomes luminous. As ions
bombard the electrode, secondary electrons
are emitted.
• These electrons impact and ionize the atoms
of the working gas. Thus more ions are
available to bombard the cathode and create
more secondary electrons
 DC Magnetron Sputtering
• In DC diode sputtering, the electrons that are
ejected from the cathode are accelerated away
from the cathode and are not efficiently used for
sustaining the discharge.
• By the suitable application of a magnetic field, the
electrons can be deflected to stay near the target
surface and by an appropriate arrangement of the
magnets, the electrons can be made to circulate
on a closed path on the target surface.
• This high flux of electrons creates a high density
plasma from which ions can be extracted to
sputter the target material producing a
magnetron sputtering configuration
• Sputter voltage
– maximize sputter yield (S)
– typically -2 to -5 kV
• Substrate Bias Voltage
– substrate is being bombarded by electrons and
ions from target and plasma
• sputtering film while you deposit
– neutral atoms deposit independently
– put negative bias on the substrate to control
this
– can significantly change film properties
• Substrate temperature
– control with substrate heater
– heating from deposited material
• increases with increasing sputter voltage
• decreases with increasing substrate bias
• Deposition rate
– changes with Ar pressure
– increases with sputter yield
• usually increases with high voltage
• Particle Energy
– increases with increasing sputter voltage
– decreases with increasing substrate bias
– decreases with increasing Ar pressure
•
•use with DC or RF
•goal: increase ionization of Ar
•Why? Higher sputter rates at lower Ar
pressures (down to 0.5 mTorr)
•fewer gas collisions - more line of sight
•How ? increase probability of electrons
striking Ar
•increase electron path length
•use electric and magnetic fields
•Most common configuration: crossed electric
and magnetic fields
•Put magnets (200 Gauss) behind target:
Magnetron sputtering cathodes use powerful magnets to confine the plasma to the
region closest to the ‘target’. This condenses the ion-space ratio, increases the
collision rate, and thus improves deposition rate.
EVAPORATION SPUTTERING

low energy atoms higher energy atoms

high vacuum path low vacuum, plasma path

•few collisions •many collisions
•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 adhesion better adhesion

(a)

Micro-pore

Droplet