Physical Vapor Deposition (PVD)

What is PVD? (main points) PVD is a process of depositing some material either atom-by-atom
or molecule-by-molecule or ion-by-ion on a solid substrate under vacuum conditions.
(Other points) PVD is fundamentally a vaporization coating technique used to form thin coatings
and can be used as an alternative to electroplating which can also be used to form thin coatings
but in an aqueous environment.

How does PVD process work? PVD processes involved four steps:
1. Evaporation. 2. Transportation, 3. Reaction and 4. Deposition
1. Evaporation: In this stage, a target, consisting of the material to be deposited is bombarded by
a high energy source such as a beam of electrons or ions. This dislodges atoms from the surface of
the target, and ‘vaporize’ them.
2. Transportation: This process simply consists of the movement of ‘vaporized’ atoms from the
target to the substrate to be coated and will generally be a straight line (line of sight).
3. Reaction: In order to coat metal oxides, nitrides, carbides, etc, the atoms from the target (pure
metal) will react with an appropriate gas during the transportation stage to form the metal oxides,
nitrides, etc. Reactive gases such as oxygen, nitrogen and methane are used for this purpose.
In cases where the coating on the substrate should be only the pure metal, then this step would not
be applicable.
4. Deposition: This is the process of coating build-up on the substrate surface. Depending on the
actual process, some reactions between target materials and the reactive gases may also take
place at the substrate surface simultaneously with the deposition process.
What are the advantages of PVD coatings?
PVD coatings are deposited to:
1. Improve hardness and wear resistance; 2. Reduce friction, 3. Improve oxidation resistance
4. To improve the performance and longevity of the mechanical components compared to uncoated
components.
5. Almost any type of inorganic and some types of organic materials can be used.
6. The process is more environmentally friendly than processes such as electroplating.
What are the disadvantages of PVD coatings?
1. It is a line-of-sight technique meaning that it is extremely difficult to coat undercuts and similar
surface features.
2. High capital cost.
3. Some processes operate at high vacuums and temperatures requiring skilled operators.
4. Processes requiring large amounts of heat require appropriate cooling systems
5. The rate of coating deposition is usually quite slow.
What are the applications of PVD coatings?
1. PVD is widely used to produce decorative coatings on plastic parts and make them look like shiny metal.
Eg. Plastic automobile parts with a PVD coating of aluminum.
2. PVD is used to apply relatively Focus on the color of each coating!
thick (1mm) coatings of heat
resistant materials on jet engine
parts. A special alloy of chromium,
aluminum and yttrium is used for
this type of coating.
3. Also used in Surgical/Medical,
Cutting tools, Fire arms, etc.
PVD is of three main types
types:: 1. Thermal evaporation; 2. Sputtering and 3. Ion plating. All these three
processes are performed under vacuum.
PVD--1: Thermal evaporation
PVD
Thermal Evaporation method involves the deposition of a thin film on a substrate according to the
following sequence of steps:
1) the material to be deposited is converted into vapor by physical means;
2) the vapor is transported across a region of low pressure from its source to the substrate; and
3) the vapor undergoes condensation on the substrate to form the thin film.
 2. PVD - Sputtering
What is Sputtering?
Sputtering is a popular method for adhering thin films onto a substrate.
Sputtering is done by bombarding a target material with a charged gas (typically
argon) which releases atoms from the target and these atoms condense over the
nearby substrate to make a thin film. It all takes place inside a magnetron vacuum
chamber under low pressure.

Sputtering process: Sputtering as a deposition technique may be described as a

sequence of these steps: 1) inert gaseous ions are generated and directed at a target
material; 2) the ions impact the target at very high-speed and sputter (release) the
atoms from the target; 3) the sputtered atoms get transported to the substrate
through a region of reduced pressure; and 4) the sputtered atoms condense on the
substrate, forming a thin film.

Materials used: PVD by Sputtering method is widely used for depositing various
metallic films (aluminum, aluminum alloys, platinum, gold and tungsten), ceramics,
metal alloys and organic and inorganic compounds on other types of substrates (like
silicon wafer used in Pentium processors).

Sputtering parameters:
1. The substance to be coated is connected to a high voltage DC power supply.
2. When the vacuum chamber has been pumped down, a controlled amount of argon
or another gas is introduced to establish a pressure of about 10-2 to 10-3 mmHg.
3. On energizing current supply, a plasma (high-energy particles) is established
between the substrate electrode (anode) and the target material be coated
(cathode).
What is a Plasma? Plasma is created by
applying an RF field to a pressurized gas
like argon, thereby creating free electrons
within the discharge region.

4. The gas atoms are ionized and they

bombard the material to be coated.

5. The energy of imposing ions cause

atoms of the target material to be
sputtered off and they are
transported through the plasma to
form a coating.

6. Direct current sputtering is used

when the target is electrically
conductive. Radio-frequency
sputtering, which uses a RF power Sputtering yield is the number of atoms ejected
per incident ion (Ar+). Sputtering yield depends
supply is used when the target is a
on 3 factors: 1) target material; 2) mass of the
non conductor such as polymer. bombarding particles; and 3) energy of
bombarding particles. Sputtering is done in the
energy range between 10 to 5000 eV.
Advantages of PVD-Sputtering over other PVD methods:
1) Sputtering can be achieved from large-size targets, simplifying the deposition of thin films
with uniform thickness over large wafers;
2) Film thickness is easily controlled by fixing the operating parameters and simply adjusting the
deposition time;
3) Control of the alloy composition, as well as other film properties such as step coverage
and grain structure is more easily accomplished than by deposition through evaporation;
4) Sputter-cleaning of the substrate in vacuum prior to film deposition can be done;
5) Device damage from X-rays generated by electron beam evaporation is avoided.
Disadvantages of PVD-Sputtering
over other PVD methods:
1) High capital expenses are
required;
2) The rates of deposition of some
materials (such as SiO2) are
relatively low;
3) Some materials such as organic
solids are easily degraded by
ionic bombardment;
4) Sputtering has a greater
tendency to introduce
impurities in the substrate than
deposition by evaporation
because the former operates
under a lesser vacuum range than
the latter
 3. PVD – Ion Plating
1. A third variation of the PVD process is ion plating (combination of thermal evaporation and
sputtering methods)
2. Metal is evaporated thermally and plasma is established to ionize the evaporating species
3. Evaporated metal ions bombard the substrate with energy
4. They physically implant into the substrate to produce an extremely strong coating bond.
5. Sputter and ion plated coatings are used in design for very thin films for electrical, optical
and wear-resistant applications.
6. The wear properties of tools are widely enhanced by hard thin film coatings.
 Chemical vapor deposition (CVD)
Chemical vapor deposition or CVD is a generic name for a group of processes that involve
depositing a solid material from a gaseous phase and is similar in some respects to
physical vapor deposition (PVD).
PVD differs in that the precursors are solid, with the material to be deposited being
vaporized from a solid target and deposited onto the substrate
In CVD, precursor gases (often diluted in carrier gases) are delivered into the reaction
chamber at approximately ambient temperatures. As they pass over or come into
contact with a heated substrate, they react or decompose forming a solid phase which
and are deposited onto the substrate. The substrate temperature is critical and can
influence what reactions will take place.
Eg. Ni(CO)4 for the deposition of Ni

Important CVD Processes:

• Atmospheric Pressure CVD
(APCVD)
• Low Pressure CVD (LPCVD)
• Metal-Organic CVD
(MOCVD)
• Plasma Assisted CVD
(PACVD)
• Laser CVD (LCVD)
CVD Apparatus
A CVD apparatus will consist of several basic components:
Gas delivery system – For the supply of precursors to the reactor chamber

Reactor chamber – Chamber within which deposition takes place

Substrate loading mechanism – A system for introducing and removing substrates,
mandrels etc

Energy source – Provide the energy/heat that is required to get the precursors
to react/decompose.

Vacuum system – A system for removal of all other gaseous species other than
those required for the reaction/deposition.

Exhaust system – System for removal of volatile by-products from the reaction
chamber.

Exhaust treatment systems – In some instances, exhaust gases may not be

suitable for release into the atmosphere and may require treatment or conversion
to safe/harmless compounds.

Process control equipment – Gauges, controls etc to monitor process parameters

such as pressure, temperature and time. Alarms and safety devices would also be
included in this category
What are the different energy sources used in CVD?
1. Resistive Heating e.g. tube furnaces
2. Radiant Heating e.g. halogen lamps
3. Radio Frequency Heating e.g. induction heating
4. UV-visible light or lasers as a source of photo energy
What are the different Precursors used in CVD?
1. Halides - TiCl4, TaCl5, WF6, etc
2. Hydrides - SiH4, GeH4, AlH3(NMe3)2, NH3, etc
3. Metal Alkyls - AlMe3, Ti(CH2tBu)4, etc
4. Metal Alkoxides - Ti(OiPr)4, etc
5. Metal Carbonyls - Ni(CO)4, etc
Essential condition for a precursor to be used in CVD:
Since materials are deposited from the gaseous state during CVD, their precursors must
be volatile and stable enough to be able to be delivered to the reactor.
Advantages
1. CVD coatings are typically fine grained and of high purity.
2. Harder than similar materials produced using conventional ceramic fabrication processes
3. CVD coatings are used to make explosion or shatter resistant glasses.
4. All surfaces in the reaction chamber get coated.
Disadvantages
1. Separate process and reaction must be developed for each coating. Some of the gases
are toxic and dangerous.
2. But greatest disadvantage is temperature should be very high at 700°C. At this
temperature, many metals soften.
 CVD Applications
1. As coatings for a variety of applications such as wear resistance, corrosion resistance, high
temperature protection, etc.
2. In the fabrication of semiconductors, integrated circuits, sensors, etc.
3. In the production of optical fibers for telecommunications.
4. To produce ceramic matrix composites such as carbon-carbon, carbon-silicon carbide and
silicon carbide-silicon carbide composites. This process is called chemical vapor infiltration
(CVI).
5. In the production of novel powders and fibers, catalysts and nanomachines.
6. A newer process known as plasma assisted CVD is used to apply diamond and diamond like
carbon (DLC) coatings.

What is the difference between PVD and CVD? PVD is similar to chemical vapor
deposition (CVD) except that the raw materials/precursors, i.e. the material that is going
to be deposited starts out in solid form in PVD. Whereas in CVD, the precursors are
introduced to the reaction chamber in the gaseous state.

Thermal evaporation is a low cost process, but all these processes are normally batch
processes because of vacuum chamber requirements.
What are the three different high-energy coating processes?
Ion implantation, laser treatment and electron beam treatment.
1. In ion implantation, ions of specific element with sufficient energy are impinged on
the surface of a material.
2. The ions so impinged are embedded into the atomic lattice of substrate. This process
is performed in a vacuum chamber.
3. Usually ion gun produce the ions. It is done by passing the gas through an electron
beam or plasma. The gas atoms on collision with the electron beam or with the
species in plasma become ions.
4. The ions are accelerated by an applied magnetic field. These ions impinge on the
work surface. The surface of the metal is hardened by creating atomic defects or
misfits by the impinged ions.
5. The depth of implantation is usually about 0.1μm. However, the sphere of influence is
much deeper, may be a micrometer.
6. Electron Beam Treatment alters the surface properties by rapid heating using
electron beam and rapid cooling in the order of 106 ºC/sec in a very shallow region
(100 µm or 0.004 in) near the surface. This technique can also be used to produce
"surface alloys“.
7. Laser Beam Treatment: This method is similar to electron beam treatment. Laser
beam treatment alters the surface properties by rapid heating and rapid cooling in a
very shallow region near the surface to produce extremely dense, crack-free and
non-porous microstructures.
Carbon dioxide (CO2) lasers are the most traditional high power lasers and are available
in power levels up to several tens of kilowatts. CO2 lasers have very high power and
power density, moderate efficiency, reliable operation and excellent beam quality.
The high wavelength of 10.6 mm results in a relative low absorption of the laser beam
by metals, e.g. steels.
 Electroplating or Electro-deposition
Define the Electroplating process: Electroplating is a process of depositing a thin layer of metal or
alloy (as anode) over another metal (as cathode) by passing a direct current (D.C.) through an
electrolytic solution containing the soluble salt of the coating metal.
What are the objectives of electroplating? Electroplating can be done on (a) metals and (b) non-
metals.
(a) On Metals: To increase the corrosion resistance of the electroplated metal; To increase chemical
resistance and wear resistance; to improve surface properties; to increase the decorative value of the
metal.
(b) On Non-Metals: For increasing strength; for decorating the surfaces of plastics, wood, glass, etc.; to
make the surface conductive by depositing a thin metal film over the non-conducting materials like
wood, glass, etc.
Characteristics and factors affecting electroplating (14 points) 1-3/4-6 points = 2 marks
1. Thickness: Thin coating for decorative and thick coating for corrosion protection purpose.
2. Adherence: Weak adherence leads to the peeling-off of the coating, usually measured by bending,
twisting, sudden heating or cooling;
3. Hardness: very important if the electroplating is done for the purpose of protection against
corrosion, measured in Brinells.
Lead coating hardness = 5 Brinells < Chromium coating hardness = 1000 Brinells.
4. Brightness: depends on surface smoothness and natural reflectance of the coated metal.
5. Protective value: depends on porosity as well as the thickness of the coating. More porosity = less
protecting power. Thicker the coating = more protecting power.
6. Decorative value: Should have good adhesion, no peel-off, should be bright, continuous and
uniform, no staining, no discoloration, no liberation of H2 gas during the cathodic deposition
which may cause blistering and pitting of the electro deposition leading to dull appearance.
7. Throwing power: It is the ability of electrolytic cell to give a deposit of uniform thickness
over the entire cathode area. Determined using Haring-Blum Cell.
Maximum throwing power (≥ 100%) is exhibited when the cathode is in regular shape.
For irregular shaped cathodes, the throwing power will be erratic (less than 100%).
Factors affecting throwing power:
i. Conductance of the bath solution: high conductance causes uniform coating even in
complex structures.
ii. Anodes: optimum placement of anodes together with the use of auxiliary anodes.
iii. Additives: use of complexing agents and leveling agents.
iv. Hydrogen evolution: Reduction in hydrogen over potential results in more uniform
coating. (x-y) * 100 %, where x = d /d and y = w /w
Determination of throwing power: 1 2 2 1
(x+y-2)
insulation
- -
electrolyte
+

d1 = 2 m d1 = 0.9 m
d2 = 1 m d2 = 1.0 m
w1 = 0.55 d1 d2 w1 = 0.65
w2 = 0.653 w2 = 0.653

68.45% 109.7%

1. w1 and w2 = weight of the metal deposited on the two cathodes.

2. When w1 = w2 then the throwing power is considered as very good (+100 %).
3. When calculated throwing power is -100%, then the coating is poor. Can be improved by
adjusting the distance of the Anode between the two Cathode electrodes.
8. Temperature:
Advantages of using Warm bath: Usual plating temperature is 35 to 60 oC. At this temperature,
(i) Solubility of electrolyte increases  Conc. of ions increases  current density increases.
(ii) Causes decrease in crystal size, thereby lowering the cost of electrical energy.
(iii) The surface diffusion is higher than hydrogen evolution thereby leading to uniform coating.
Disadvantages of using very high temperature bath: Hydrogen evolution may take place
leading to the corrosion of equipment and also decomposition of the organic additives.

9. Agitation: Excessive agitation leads to rough deposition, decrease in throwing power,

increase in bath temperature.

10. Cleaning of the article to be plated: Why? A well cleaned and properly pre-treated
surface of any base material, if electroplated, may form a protective coating of long life.
The base metal should (a) be free from dirt, grease and corrosion products (oxides, sulphides).
(b) Have uniform, less porous/more smoothness physical structure.

11. Composition of the electrolytic bath:

solution:: ideal conc. is about 1-3 mol L-1. If the metal-ion
(a) Plating metal ion salt solution
concentration is higher, then the mass transfer process of the metal ion is decreased resulting in
poor quality of the coatings.
Non-participating electrolytes added to increase the conductivity of the bath.
Non-participating electrolytes also act as buffers to control the pH.
Inert electrodes used to increase the conductivity of the bath.
 agents:: On complexing the metal ion with a complexing agent (like CN-), fine
(b) Complexing agents
grained and more adherent coating deposits are obtained. How they work?
Complexing agents are used to:
(i) avoid the reaction between cathode base metal and coating metal ions
Fe + Cu2+  Fe2+ + Cu
CN- ion complexed with Cu2+ ion will inhibit the above reaction.
(i) make the potential of the coating metal ions more negative in order to carry out the coating
at a lower potential.
(ii) avoid the passivation of anodes so that they are dissolved more easily.
(iii) enhance the throwing power of the plating bath solution.
Examples of complexing agents: cyanide, sulphamate, hydroxide, etc. CN- gives smooth
and adherent deposits of Cu, Ag, Au, Cd, Zn, etc.
(c) Organic additives
additives::
(i) Brighteners: produce “microscopic fine deposits” which reflect the light falling on the
surface. Brighteners plate parallel over the metallic surface and inhibit the perpendicular
plating over the surface.
Examples of Brighteners used: Aromatic sulphonates or sulphones, compounds containing –CN,
C=O, -N=C=S group (Coumarin, thiourea).
(ii) Levelers: The function of a leveler is to produce a level deposit by getting itself
adsorbed at regions where rapid diffusion of ions may occur.
For Ni plating, sodium allyl sulphate is used as a leveler.
(iii) Structure modifiers: also called as stress relievers.
(iv) Wetting agents: are added to release the gas bubbles (H2) from the surface of the
cathode. Eg. Sodium lauryl sulphate (a synthetic detergent).
12.. Current density
12 density:: Current density is adjusted to get an adherent film.
What is an Adatom? = adsorbed atom; Single atoms lying on surfaces.
A cluster of atoms, or a molecule or cluster of molecules lying on surfaces = Adparticle.
This is often a thermodynamically unfavorable state.
(a) At low current density: uniform deposit is obtained.
(b) On increasing the current density: less ordered deposit is obtained.
(c) At very high current density below limiting values: poorly adherent, rough and powdery
textured deposit is obtained.
(d) At very high current density above limiting values: evolution of hydrogen predominates,
leading to the formation of dispersed deposits (containing metal oxides and hydroxides).

13.. Choice of the electrolyte

13 electrolyte:: should be a good conductor, highly soluble, should not undergo
hydrolysis, oxidation, reduction and other chemical changes. It should possess sufficient
covering power.
No single electrolyte satisfies all the above requirement. Usually a mixture of electrolytes are
used. Eg. In Copper plating, CuSO4 is used along with dil. H2SO4.

14.. pH of the bath liquid

14 liquid:: For a good electro-deposit, the pH of the bath must be properly
maintained. For most plating baths, pH ranges from 4 to 8. maintained using buffers.
pH lower than optimum value = evolution of H2
pH higher than optimum value = precipitation of metal hydroxides on the electrode surface.
What is the importance of cleaning the metallic articles before electro-deposition?
1. Solvent Cleaning: using organic solvents like toluene, acetone, CCl4, xylene, etc.
This is followed by cleaning the substrate with steam and hot water containing wetting agents
and alkalis.
This treatment provides a base metal surface which can be readily wetted by aqueous
solution, which is the pre-requirement for any electroplating process.
2. Alkali Cleaning: used for removal of old paint coating from the metal surface. Eg.
Trisodium phosphate, caustic soda. Always followed by thorough rinsing with water and
then immersion in slightly acidic solution of 0.1% chromic acid to Na/K dichromate to
remove the last traces of alkali.
3. Mechanical Cleaning: is done by hand cleaning using a wire brush + some abrasive
(sand) and detergent (soap) to remove loose rust and other impurities from the metal
surface. The remaining dust are then removed by solvent cleaning followed by steam or
hot water treatment.
4. Flame Cleaning: is done by heating the metal surface with a hot flame to remove
moisture and other loosely adhering scales followed by wire-brushing.
5. Sand-blasting: used when a slightly roughened surface is desired. Process consists of
introducing sand (as an abrasive) into an air stream, under pressure of 25 to 100 atm.
The sand blast impact removes any scale present and also hardens the cleaned metal
surface. Usually suited for cleaning large steel surfaces. However, the process is
dangerous to the workers involved since it leads to an disease called “silicosis” which
affect the lungs.
6. Pickling and Etching: Acid pickling is more convenient than mechanical and sand-blast
cleaning. Metal is immersed in acid bath except Al which is immersed in alkali bath.
Acid pickling of steel in warm dil. H2SO4 or cold dil. HCl in the presence of an inhibitor.
The cleaned surface is smooth, tough and bright in appearance.
 Plating bath solution
The concept of reversing the direction of the spontaneous reaction in a galvanic cell
through the input of electricity is concept behind the electroplating method.
Electroplating setup involves the following components:
1. Plating Tank: Normally plating is carried out in rectangular tank made of wood or steel with a
ceramic or polymer layer inside so as to provide thermal insulation. The volume varies between 25
to 2000 L.
2. Plating bath solution: A highly conducting salt solution of the metal is used for electro-plating.
Non-participating electrolytes are added to the bath solution to increase the conductivity and the
throwing power.
Buffer and other additives are added to maintain the pH and to get bright and compact deposits.
The level of the plating bath should cover completely the cathode and sufficient area of anode.
Mixture of two or more electrolytes is used for preparing electrolytic bath.
3. Heating arrangement: Heating if required is provided by heating coils or
hot gases.
4. Convection arrangement: Air sparger (if oxygen does not interfere) or
nitrogen sparger is employed to introduce convection current in the
plating bath solution.
5. DC voltage arrangement: DC source is used for electroplating with a
voltage of 8-12V and a current density of 1-200 mACm-2. For initial
nucleation, high over potential is required.
6. Provision of Filters: In large plating operations, pumps and filters are
employed to filter out regularly the metallic particles (dust or grit) which
may hinder in smooth deposition. The anode sludge is retained by the
anode in cotton bags.
7. Power supply to the electrodes: Copper, brass or Al bus bars are usually employed for supplying
the power to electrodes. The anodes and cathodes are suspended alternatively from the bus bars
through the entire width of the tank. Usually, anodes are made of the plating metal, but in some
cases insoluble anodes are used.
Anodes can be rod type, plate type or even as pellets kept in mesh basket. Cathodes are either
articles to be electroplated or jigs connected to the bus bars.
8. Pretreatment of cathodic surface: (a) removal of organic impurities using organic solvents; (b)
Acid pickling using dil. H2SO4; (c) Polishing: using silicon carbide wheels followed by sand
blasting and/or mechanical buffing; (d) Rinsing in water followed by drying.
9. Process of electroplating: Anodes connected to positive; Cathodes connected to negative
terminals.
The thickness of the deposit ranges from 0.01 to 100 mm. Time = few seconds to 30 minutes.

Compare Galvanic Cell and Electroplating Cell:

Refer to the diagram in
J & J book
 Let's assume it takes 1.0 g of gold to provide an
adequate coating for our glasses and also assume that
we are using an EMF sufficient to produce 10 amperes
(A) of current (1 A = 1 coulomb per second). how long it
will take to plate that 1.0 g of gold?

The above problem only involves the use of unit cancellation. To calculate the time
needed to deposit a certain amount of material, you need to start with the amount,
converted to moles (197 g AU = 1 mol, then 1 g Au = ?).
Then, multiply by number of electrons consumed in the reduction (3 mol e -/1 mol Au).
Using the definition of a faraday, 96500 C/mole of electrons.
Finally, by using the definition of an ampere, 1 Amp = 1 C/sec.
There are various ways of phrasing this same problem such as "how much gold is
deposited in 146 seconds at 10 A" or "what current is required to deposit 1.0 g of gold in
146 seconds.

JUST FOR YOUR UNDERSTANDING – NOT FOR THE EXAMS!!!