PP UNIT 4 PVD CVD Edited

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RV College of
Engineering Go, change the world
RV College of
Engineering
Dept of Mech. Engg.
UNIT –IV
Physical Vapour Deposition
Sputtering
Arc Evaporation (cathodic arc deposition)
Chemical Vapour Deposition
Dr. H N Narasimha Murthy
Professor and Dean – R & D
Department of Mechanical Engg
RV College of Engg., Bengaluru
RV College of
Engineering Vapour Deposition Techniques Go, change the world
There are two primary techniques for layer deposition :
1. Physical Vapor Deposition (PVD)
2. Chemical Vapor Deposition (CVD)
Vapour deposition (either physical or chemical) is a coating process, where coating

material is condensed in vacuum at the substrate from vapour phase, forming a thin
(≤ 10 μm in case of physical deposition and ≤ 1000 μm in case of chemical
deposition) film. Generally metals and non-metals can be deposited.
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Engineering
Deposition Processes
Process type Material is introduced in
Thermochemical Solid / liquid / gaseous form (diffusion)
Chemical Solution form(electrochemical)
Electrodeposition Solution form(electrolysis)
Hot-dip Liquid melt
Cladding Solid form
Sol-gel Solution form
Thermal spraying Liquid form
Vapor deposition Vapor (gaseous) form only
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Engineering
Comparison of the Coating Processes
RV College of
Engineering
Physical vapor deposition (PVD) refers to a family of processes in which a material is

converted to its vapor phase in a vacuum chamber and condensed onto a substrate surface as a
thin film.
PVD can be used to produce coatings of a wide variety of materials:

 metals
 ceramics
 semiconductors
 polymers
 Alloys
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Engineering Physical Vapour Deposition
Features of PVD
Absence of chemical reaction during the deposition process;
Relatively low temperatures (250 … 600 ºC) in comparison with CVD processes;
Electric [and magnetic] field is applied;
PVD technologies can be classified into three types:

Evaporation,
Sputtering and
Arc Evaporation
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PVD process steps
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Engineering
All PVD processes consist of the following steps:

 synthesis of coating vapour
 vapor transport to the substrate
 condensation of vapors onto the substrate surface to form a thin film.
These steps are carried out inside a vacuum chamber, so evacuation of the chamber
always precedes the PVD process.
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Engineering
The two most common PVD processes are:

 evaporation (vacuum chamber is ~10-6 Torr (~10-4 Pa) or lower)
 sputtering (vacuum chamber is typically 10-3 to 10-2 Torr (~1 Pa))
1 Torr = 10-3 bar
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Evaporation in PVD
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Engineering
In order to evaporate a material, it must be heated to a temperature at which its vapour pressure is
10-3 Torr or higher. e.g., aluminum must be heated to 1000 C or higher
There are two common ways to heat the source material:

 resistive heating
 electron-beam heating / Laser beam evaporation
Resistive heating uses electric current flow through a tungsten filament to heat the source material.
The source material can be placed directly on the tungsten filament, or it can be put in a crucible that
is heated by the filament.
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Thermal Evaporation
The Coating Material is resistance heated up
to the evaporation temperature, and atoms of
the material move towards the substrate by a
straight trajectory and deposit on it, producing
a film. Only metals and metal alloys with a low
melting points can be applied (e.g. Zn, Al, etc.)
Thermal Evaporation is used for metallization
of fabrics.
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RV College of
Engineering Electron-beam (e-beam) evaporation Go, change the world
In electron-beam (e-beam) evaporation, a high intensity beam

of electrons, with energy up to 15 keV, is focused on the
source material.
Electron bombardment heats the source material to the

temperature required for evaporation. Heating can be restricted
to the source material itself. The surroundings stay cool.
Because of high vacuum pressure in the vacuum chamber, the

source material travels in a straight line from the source to the
substrate.
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Engineering Laser Beam Evaporation
Target (coating material) ablated by focused laser beam.

Ablated atoms / atom layers travel through vacuum chamber
and deposit at substrate.
All metals, metal alloys, ceramics and polymers can be
Target (coating) materials. Process temperature is RT.
But, Laser gun is cost inhibitive.
Application: magnetic data storage media production,
Ultra-high rate aluminization of fabrics and transparent
barrier coatings.
Pulsed Laser Deposition
Engineering
. Sputtering is achieved by bombarding the target

with energetic ions, typically Ar+.
Surface atoms of the target are dislodged by this

bombardment and fly off .
These atoms then impinge on the substrate,

resulting in deposition of a thin film.
In PVD sputtering, the Target is usually in the form

of a sheet or plate
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Engineering
Sputtering – General Principles

Low vacuum (0.0005 … 0.12 torr ↔ 0.07 … 16 Pa) with the presence of inert gas atoms
(usually Argon);

High voltage (1 to 5 kV) applied between the target (sputtered material) and the substrate;

Due to high voltage, the inert gas atoms ionize, forming a plasma cloud near the surface of
sputtered material;

The ions become accelerated in the electric field between the substrate to be coated and
target of the sputtered material;

Sputtered material is bombarded by accelerated inert gas ions from a plasma cloud, which
is situated close to its surface;

As a result, atoms and atomic layers are extracted from the sputtered material, which are
directed to the substrate; sputtered atoms form a coating.
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Engineering
Sputtering Technologies
1. Direct current (DC) diode sputtering (direct voltage is applied between the target (cathode)
and substrate (anode));
2. triode sputtering (heated filament is used as a source of secondary electrons to help ignite
and sustain the plasma);
3. radio frequency (RF) sputtering (an alternative voltage at a high frequency (~13.6 MHz) is
applied between the target and the substrate);
4. magnetron sputtering (an electron trap is formed by magnetic fields, what make electrons,
extracted during the ionization and bombardment process, to arrive back at the target).
If the sputtered and deposited material further reacts with gases,
. the process is called reactive sputtering
Engineering
Sputtering Technologies – Magnetron Sputtering

distinct advantages of magnetron sputtering in comparison with other sputtering
technologies are higher deposition rates (10 times greater than that of DC diode sputtering)
and lower substrate heating;

both DC and AC current sources can be applied for magnetron sputtering (in other words,
it can be either direct current magnetron sputtering or RF magnetron sputtering);

Magnetron Sputtering is used in semiconductor industry, tool industry, etc..
.
Engineering
Magnetron Sputtering Process

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Mean free path of atoms in PVD
The mean free path is the average distance between collisions in the chamber.
The mean free path, , l of atoms or molecules in a chamber at pressure P is given by
kT
 2
2 Pd
T is the absolute temperature, k is Boltzmann’s constant, and d is the diameter of the gas
atoms or molecules
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Engineering
Mean free path of atoms in PVD
At room temperature and for a typical atom/molecule of diameter 4 Å, the previous

3
equation becomes 5.8  10
 ( m)
P
The pressure P is in pascal (Pa).
1 Pa = 1 N/m2 = 7.5 x 10-3 Torr

What is the mean free path for typical evaporation and sputtering conditions?
24
Engineering
Vapour Deposition Process Application Fields

†
electrical devices (LCDs, touch panels, microelectronic devices, solar cells, etc.)
†
magnetic devices (magnetic storage media)
†
optics (laser mirrors, antireflection coatings, etc.)
†
tool industry (plastic molds, cutting tools, blanking tools, etc.)
†
aerospace devices (turbine blades, etc.)
†
decorative purposes (watches bands, etc.)
25
Engineering
Vapour Deposition Process Limitations

The coatings are very thin, they can't improve bulk properties (tensile strength, fracture
toughness, etc.), that is why good mechanical properties of the substrate are needed;

As vapour deposition is mostly a high-temperature process, the ability of the substrate
to withstand high temperatures is required;

Vapour deposition is a low production process;

Vapour deposition equipment is relatively expensive
26
Engineering Advantages of PVD Coatings
 Application: Aerospace, cutting tool and energy production industries

 Preferred due to high quality of coatings produced
 Does not produce harmful by-products that can damage the environment
 Unlike electrodeposited coating procedures it does not have outputs that must be treated/
contained after completion
 Even CVD process produces toxic vapours that can be extremely harmful; coupled with this
problem is the costs incurred for safe disposal of these chemicals and gasses, which can be
significant and complicate the production line
 Wide range of applications : wear resistance, corrosion resistance, electronic and optical
27
Engineering
Cathodic Arc Evaporation – General Principle

High-current low-voltage strikes at the surface of the target (Coating material)

Due to arc striking, a highly energetic emitting area (so-called cathode spot) appears
at the surface of the target;

Temperature inside the cathode spot is extremely high (around 15000 ºC), causing the
evaporation of the target material with the formation of a highly ionized quasi-plasma cloud;

This quasi-plasma cloud is directed towards the substrate and is deposited onto it,
forming a film;

if necessary, a reactive gas is introduced after this, so that gas molecules react with the
deposited film, creating a coating.
.
Engineering Schematics of Cathodic Arc Evaporation Process
.
Engineering
Cathodic Arc Evaporation – Technological Features

Comparison with other PVD technologies, arc evaporation is the most productive one;

allows to deposition of denser coatings with highest mechanical properties;

highest target utilization among the PVD technologies;

main disadvantage - formation of macrodroplets during the evaporation, leading to higher
surface roughness of the coatings (highest of all PVD technologies), and lowers their
adhesion to the substrate;
Engineering
Comparison of PVD Technologies
Process Deposition rate, Pressure, Pa Particle energy, eV Adhesion

μm/s
Evaporation 0.05 … 25 10-3 <2 +
Sputtering* 0.0001 … 0.7 10-1 ... 10 10 … 100 ++
Arc 0.0003 … 1.85 0.5 ×10-2 … 10 … 100 +++

evaporation 1.5×10-2
Engineering
Chemical Vapour Deposition (CVD)
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Engineering schematics of CVD
Engineering
Four stages of CVD
CVD includes wide range of technologies of vaporizing a metal and using chemical reactions
at the substrate.
Four Stages in CVD deposition:
1. Formulation of the reactant vapour,
2. Transport of this vapour,
3. Chemical reaction between vapour & heated substrate
4. Finally removal of by-products.
CVD is carried out in a contained vessel or reactor due to the volatile nature of the chemicals
involved.
Pressure in the vessel is atmospheric or below it.
Temperature in the reactor can reach up to 1500 C.
Engineering
CVD for deposition of TiC
Chemical reaction i) for depositing TiC: TiCl4 + CH4 + H2 (1030C) → TiC + 4 HCl + H2.
ii) For depositing TiN: TiCl4 + N2 + H2 (1000C) → TiN + 4 HCl + H2.

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Engineering
CVD Coatings in Metal-Forming Application
CVD coatings are used in many manufacturing applications as a wear-resistant coating:

carbide milling and turning inserts, wear components, some plastic processing tools, etc.
Most common application for CVD coating is for metal-forming tools. CVD coatings
provide excellent resistance to the types of wear and galling typically seen during many
metal-forming applications.
In high stress metal-forming applications, where the tool’s tolerances and substrate
permit, high temperature CVD coating processes will perform better than “cold” processes
like PVD, thin-dense chrome (TDC), nitriding, etc. The chemical/metallurgical bonding that
results from the CVD coating process creates adhesion characteristics that simply cannot
be duplicated by a “cold” process. This enhanced adhesion protects forming tools from the
sliding friction wear-out caused by the severe shearing stresses generated in heavy metal-
forming applications. 41
Engineering
Chemical Vapor Deposition (CVD) PPT, Principle, CVD Process, Variables, Advantages, Applications - Melezy
Engineering
End of CVD……
Thank You for your kind attention
43
Engineering Metal Organic Chemical Vapour Deposition (MOCVD)
Metallo-organic CVD (MOCVD) is a specialized area of CVD, (introduced in 1960s for

the deposition of indium phosphide and indium antimonide.
Experiments demonstrated that deposition of critical semiconductor materials can
be obtained at lower temperature than conventional thermal CVD and that epitaxial
growth can be successfully achieved.
The quality and complexity of the equipment and the diversity and purity of the
precursor chemicals have steadily improved since then and MOCVD is now used on a
large scale, particularly in semiconductor and opto-electronic applications.
RV College of
Engineering
Metal Organic Chemical Vapour Deposition (MOCVD) Go, change the world
Metallo-organics are compounds in which the atom of an element is bound to one or more
carbon atoms of an organic hydrocarbon group.
Many of the elements used in MOCVD are the metals of groups IIa, IIb, IIIb, IVb, Vb, and VIb,
which are non-transitional. The metallo-organics thus complement the halides and carbonyls,
which are the precursors for the deposition of transition metals (Groups IVa, Va, and VIa) and their
compounds.
The term metallo-organic is used somewhat loosely in CVD parlance, since it includes compounds
of elements, such as silicon, phosphorus, arsenic, selenium, and tellurium, that are not considered
metallic. To conform to what appears to be a well-established tradition, such nonmetal
compounds will be included here as metalloorganics.
RV College of
Engineering
RV College of
Engineering
Most MOCVD reactions occur in the temperature range of 300 to 800 C and at pressure
varying from less than 1 Torr to atmospheric.
Because of the highly critical requirements of most semiconductor applications, it is
necessary to use the most accurate controls and high-purity reactants. Electronic mass-
flow controllers, ultrafast bellow-sealed gas-switching valves, accurate venting controls,
and complete elimination of dead space allow rapid switching of gases.
As a result, deposits of less than 10 nm in thickness and with abrupt interfaces of less
than 1 nm can be produced. The equipment and chemicals used in MOCVD are all
available commercially but are expensive and production cost is high. For these reasons,
MOCVD is considered in applications where high quality is essential.
Engineering Schematics of a typical MOCVD system
A typical reactor for the deposition of the optoelectronic material gallium-aluminum-arsenide

Engineering Metal Organic Chemical Vapour Deposition (MOCVD)
To be useful as CVD precursors, a metallo-organic compound should be stable at room

temperature so that its storage and transfer are not a problem. It should also decompose
readily at low temperature, i.e., below 500 C.
Hydrides of arsenic and phosphorus are often preferred as CVD precursors. These
hydrides however are extremely toxic and environmental considerations may restrict
their use.
The compounds which meet these conditions are listed.
RV College of
Engineering
Engineering
End of MOCOD

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Go, change the world

Dept of Mech. Engg.

There are two primary techniques for layer deposition :

1. Physical Vapor Deposition (PVD)

2. Chemical Vapor Deposition (CVD)

Vapour deposition (either physical or chemical) is a coating process, where coating

Physical vapor deposition (PVD) refers to a family of processes in which a material is

PVD can be used to produce coatings of a wide variety of materials:

Absence of chemical reaction during the deposition process;

Electric [and magnetic] field is applied;

PVD technologies can be classified into three types:

All PVD processes consist of the following steps:

 vapor transport to the substrate

 condensation of vapors onto the substrate surface to form a thin film.

The two most common PVD processes are:

 sputtering (vacuum chamber is typically 10-3 to 10-2 Torr (~1 Pa))

1 Torr = 10-3 bar

There are two common ways to heat the source material:

 electron-beam heating / Laser beam evaporation

In electron-beam (e-beam) evaporation, a high intensity beam

Electron bombardment heats the source material to the

Because of high vacuum pressure in the vacuum chamber, the

Target (coating material) ablated by focused laser beam.

. Sputtering is achieved by bombarding the target

Surface atoms of the target are dislodged by this

These atoms then impinge on the substrate,

In PVD sputtering, the Target is usually in the form

Magnetron Sputtering Process

The mean free path, , l of atoms or molecules in a chamber at pressure P is given by

At room temperature and for a typical atom/molecule of diameter 4 Å, the previous

The pressure P is in pascal (Pa).

1 Pa = 1 N/m2 = 7.5 x 10-3 Torr

Vapour Deposition Process Application Fields

Vapour Deposition Process Limitations

 Application: Aerospace, cutting tool and energy production industries

Cathodic Arc Evaporation – Technological Features

Comparison of PVD Technologies

Process Deposition rate, Pressure, Pa Particle energy, eV Adhesion

Evaporation 0.05 … 25 10-3 <2 +

Sputtering* 0.0001 … 0.7 10-1 ... 10 10 … 100 ++

Arc 0.0003 … 1.85 0.5 ×10-2 … 10 … 100 +++

Chemical Vapour Deposition (CVD)

ii) For depositing TiN: TiCl4 + N2 + H2 (1000C) → TiN + 4 HCl + H2.

CVD Coatings in Metal-Forming Application

CVD coatings are used in many manufacturing applications as a wear-resistant coating:

Thank You for your kind attention

Metallo-organic CVD (MOCVD) is a specialized area of CVD, (introduced in 1960s for

A typical reactor for the deposition of the optoelectronic material gallium-aluminum-arsenide

To be useful as CVD precursors, a metallo-organic compound should be stable at room

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