SURFACE ENGINEERING OF NANOMATERIALS

Lecture 12: Physical Vapour Deposition (PVD)

Dr. Kaushik Pal

Associate Professor
Dept. of Mech. & Indl. Engg.
Joint faculty: Centre of Nanotechnology
Introduction:
 PVD involves physical ejection of material as atoms or molecules; and condensation and
nucleation of these atoms onto a substrate.
 The vapor phase material can consist of ions or plasma and is often chemically reacted
with gases introduced into the vapor, called reactive deposition, to form new compounds.

 These processes can be applied to various kinds of

ceramic, polymers, alloys and composites etc.

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Classification of PVD:
Thermal Evaporation

Physical Vapor Deposition

Electron Beam (e-beam) Evaporation

Reactive /Activated Reactive Electron Beam Evaporation

Sputtering

Filtered Cathodic Arc Deposition

Ion Plating

Pulsed Laser Deposition

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Thermal Evaporation:
Process:
 A thermal evaporator uses an electric resistance heater to melt the
source material and raise its vapor pressure to a useful range.
 Thermal energy is imparted to atoms in a liquid or solid source so that
it can efficiently evaporate.
 Evaporation takes place in vacuum (generally, 10-4 to 10-6 Torr).
 Evaporated particles can travel directly to the deposition target
without colliding with the background gas.
 Films can also be co-evaporated using multiple sources.

Types of thermal evaporation according to input energy:

Laser
Direct Indirect
Inductive ablation/
resistive resistive
heating laser
heating heating
evaporation

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1. Direct resistive heating:
• Evaporation materials direct evaporated by high electric current.
• These materials can be in the shape of wire or rods.
• It is limited to few materials e.g. C, Cr, Fe, Mo, Ni, Pd, Rh, Ti, Al.
2. Indirect resistive heating:
• The evaporation material is put into a container (called "boat"),
spiral wire, ribbon or crucible.
3. Inductive heating:
• The evaporated material is heated by high or low frequency induction.
• The evaporated material has to be conductive.
4. Laser evaporation/ Laser ablation:
• The continuous interaction of laser radiation with matter can lead
to thermal evaporation.
• In alternative mechanisms, particles may be released from the solid
due to low pulse duration and high power density of incident
radiation.
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 Optimization:
Advantages:
• Purity of the film depends on the purity of the
 Simple and cheap
source material and the quality of the vacuum
 Less surface damage of the substrate
• In case of films, the thickness of film vary
 Excellent purity of films
according to the geometry of chamber

Disadvantages: Applications:
 Limited to low melting point metals  Evaporation of metals, alloys,
 Poor density and adhesion semiconductors, insulators etc.
 It’s not possible to evaporate the dielectric  Gold plating machine
materials  Thermal insulation coatings
 Filament limits the amount of materials that
can be deposited
 Step coverage is more difficult to improve
Thermal insulator coating

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Electron Beam (e-beam) Evaporation:
Process:
 A target anode is bombarded with an electron beam given off by
a charged tungsten filament under high vacuum.
 Atoms from the target transform into the gaseous phase due to
the electron beam.
 These atoms then precipitate into solid form by coating the
substrate with a thin layer of the anode material.

Advantages: Applications:
 High (few μm/min) as well as low (1 nm/min) deposition rate. Aerospace, Cutting and Tool
 Ability to control structural and morphological properties of industries, Electronic & Optical
films for semiconductor industries.
films.

Disadvantages:
 Filament degradation due to a non-uniform evaporation rate.
 Significant scattering of the vapor cloud takes place.

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Reactive and Activated Reactive Electron Beam Evaporation:
Purpose of reactive and activated reactive electron beam:
 Certain refractory oxides and carbides undergo fragmentation during electron beam evaporation,
resulting in stoichiometry which is different from initial material.
 To overcome this situation, reactive/activated reactive evaporation are employed.
 Both e-beam and thermal evaporation processes are used for reactive/activated reactive deposition.

Advantages: Deposition of oxides (compounds)

Reactive type:
 In this process, the reactive gas (O2, N2, Hydrocarbon) is
introduced into the chamber while the metal is evaporated.

 When the thermodynamic conditions are met, the metal atoms

react with the gas in the vicinity of the substrate to form films. Reactive evaporation process
of Al with oxygen gas

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Activated Reactive type (ARE):
 This process is two-fold:
 To enhance the reaction efficiency through activation of the
reactive gas that are necessary for deposition of compound films.
 To modify the growth kinetics and hence the
structure/morphology of the deposits.
 Plasmas are also used to activate the reactive gas.
 Its evaporation sources may be
• e-beam evaporation source
• A resistance-heated source.
 Recent developments in the ARE process
1. To produce the vapor species.
2. Confinement of evaporation techniques and development Carbide coated cutting tools
of modified plasma excitation geometries.
 Applications:
 TiO2, SiO2 as optical coatings
 Manufacturing of Carbides and Nitrides (TiC, TiN).

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Sputtering:
• Steps for sputtering process:
1. Target material and substrate is placed in a vacuum chamber.
2. A voltage is applied between target (cathode) & substrate (anode).
3. A plasma is created by ionizing a sputtering gas (generally a
chemically inert, heavy gas like Argon).
4. Atoms/molecules of target material are ejected into a gas form or
plasma due to bombardment of sputtering gas.
5. Ejected target materials deposited onto the substrate.
• For efficient momentum transfer, the atomic weight of the sputtering
gas (Ar, Ne, Kr, Xe) should be close to the atomic weight of the target.
Advantages:
 Materials having high melting points can be easily sputtered.
 Films by sputtering have a better adhesion on the substrate than evaporated films.
Disadvantages:
 Inert sputtering gases are built into the growing film as impurities.

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Comparison between Evaporation and Sputtering processes:

Evaporation Sputtering
Low energy atom (0.1 eV) High energy atom/ ions (1-10 eV)
• Denser film
• Smaller grain size
• Better adhesion
High vacuum Low vacuum
• Directional, good for lift-off • Poor directionality, better step coverage
• Lower impurity • Gas atom implanted in the film
Point source Parallel plate source
• Poor uniformity • Better uniformity
Component evaporate at different rate All component sputtered with similar rate
• Poor stoichiometry • Maintain stoichiometry

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Cathodic Arc Deposition:
 An electric arc is used to vaporize material from
target cathode. Vaporized material then condenses on a
substrate, forming a thin film.
 Cathodic arcs take a special place among PVD
processes because of high ion densities.
Cathodic arc deposition process
 Arc vaporization occurs when a high current (low
voltage) is passed through a source material placed
Issues faced by the cathodic arc
between two electrodes (anode and cathode).
process:
 This process produces extremely hard films therefore • Poor film quality
can be used for thin hard-film, super hard • Uniformity in thickness
coatings or nanocomposite coatings. • Poor arc control
• Poor repeatability & reliability for
 It can be used to deposit metallic, ceramic, production processes
and composite films. • High maintenance

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Filtered Cathodic Arc Deposition:
 The filtered cathodic arc (FCA) process is extensively used
to deposit tribological and wear resistant thin films.
 Mainly, it eliminates the macroparticles that degrade coating
performance.
 Ejected particles are fed into a curved duct having a focusing
magnetic field and a steering field which separates the
particles by mass, thus "filtering" them (like a mass
spectrometer).
 Unwanted macroparticles and neutral atoms are filtered out
by mechanical filters, and coating species reaching the
substrate are pure ions. Filtered cathodic arc deposition
process
 The beam of particles must be rastered over the substrate to
coat large areas with acceptable uniformity.

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Ion Plating:
 It is an atomistic vacuum coating process where depositing film is
continuously or periodically bombarded by energetic atomic-sized inert
or reactive particles.
 It is also called as ion assisted deposition (IAD) or ion vapor
deposition (IVD).
 Activated reactive evaporation (ARE) process with a negative bias on
the substrate is called reactive ion plating.
 The source of depositing atoms can be from vacuum evaporation,
sputtering, arc vaporization or from a chemical vapor precursor.
 Mechanism of Ion-plating: Evaporation Sputtering Arc vaporization

1. Surface preparation
2. Nucleation and interface formation
3. Film growth.
Sources of depositing atoms

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Types of ion-plating process:
1. Plasma based ion plating: Bombarding species are generally
accelerated ion from a plasma.

2. Vacuum based ion-plating: Bombarding species are accelerated

ions from an ion source in vacuum chamber. Plasma based ion plating

Advantages:
 Compatible with any PVD and many CVD processes.
 Most advanced surface finishing process.
 This process makes the gold or other metal coating more
durable, more wear resistant and higher brightness.
Vacuum based ion plating
 Possibility of high density films.
 Excellent adhesion of films to the substrate. Disadvantages:
 Possibility of unwanted substrate heating
 Introduced by plasma bombardment

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Pulsed Laser Deposition (PLD):
 A high-power pulsed laser is focused on the target which is ablated
to form a plume of atoms, molecules, and particulates directly
towards the substrate.
 It can work under controlled gas environment (both inert and
reactive)
 Mechanism of PLD:
The mechanism of the PLD process can be expressed in three steps:
• The interaction of the laser beam and target.
• Plasma plume formation
• Nucleation and growth of thin film
 Some factors that influence the deposition rate:
• Target material
• Pulse energy of laser
• Distance from target to substrate
• Type of gas and pressure in chamber (oxygen, argon, etc.)

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Benefits over other film deposition methods: Disadvantages:
• Fast response, well controlled deposition rate. • High defect or particulate
• Relatively high deposition rates (~100s Å/min). concentration.
• Growth in any environment. • Uneven coverage.
• Flexible, easy to implement. • Not well suited for large scale film
• Reproduce the composition of the target. growth.
• Used to deposit Multilayer films. • PLD does not fit every application.
• Deposition of highly crystalline films.

Applications:
 Dielectric and ferroelectric films
 Optical and tribological coatings
 Semiconductors
 Architectural structures
 Window glazing
 Vacuum web coating
 Wear resistant coatings

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Summary:
 In PVD, chemical reaction are not involved except for reactive sputtering
deposition.
 The main advantages of PVD are
• Controllable growth of thin films with high purity.
• Ability to control structural and morphological properties of films.
• Improvement in repeatability and reliability of the modified substrate.
• In most cases, instruments are highly precise as well as cost effective.
 Modification techniques can be applied in various fields like manufacturing of
semiconductor devices, optical coatings, tribological coatings, aerospace
industries etc.

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