Thin film growth

The vapor-based thin film synthesis methods are classified as either physical vapor deposition (PVD) or
chemical vapor deposition (CVD)
 In PVD, a solid sample containing the target elements is subjected to
substantial energy, often in the form of a plasma or an electric
discharge, thereby ejecting atoms and producing a vapor, which can
then condense onto the substrate.
 In CVD, target elements are delivered in the form of volatile molecules,
denoted as precursors, and the film is built up via a series of chemical
reactions between precursors, precursor fragments and the substrate.
 Chemical vapour deposition (CVD)
The Chemical vapour deposition (CVD) is a process where one or more volatile
precursors are transported via the vapour phase to the reaction chamber, where
they decompose on a heated substrate.
In the broadest sense chemical vapour deposition (CVD) involves the
formation of a thin solid film on a substrate material by a chemical reaction of
vapour-phase precursors.
The precursor molecules are
often diluted in a carrier gas
that makes up the main part
of the gas volume in the
process. The carrier gas in
CVD is most often hydrogen,
nitrogen or argon, or mixtures
of these.
Schematic drawing of the assembled CVD setup used for the synthesis of graphene films.
Classification of Chemical Vapor Deposition
CVD has been classified by three parameters:
1. operating conditions: (i) atmospheric pressure CVD (APCVD), (ii) low-
pressure CVD (LPCVD), and (iii) Ultrahigh vacuum CVD (UHVCVD);
2. physical characteristics of vapor: (i) aerosol-assisted CVD (AACVD)
and (ii) direct liquid injection CVD (DLICVD); and
3. substrate heating: (i) hot wall CVD and (ii) cold wall CVD.

Or Generally it may classified, into three types:

1- Thermal CVD (heating the gas and/or the substrate)
2- Plasma CVD (excitation by electrons in a plasma where the electrons
are accelerated by an electric field)
3- Laser CVD (excitation by light source, laser or broadband)
CVD Classification by pressure regime are
-Atmospheric pressure (APCVD) (760 Torr),
-Low pressure CVD (LPCVD) (0.01-10 Torr),
-Ultra High Vacuum CVD (UHV-CVD) (10-6-10-3 Torr)

CVD sometimes classified by film structure or growth mechanism, and

described as Epitaxy or Vapor Phase Epitaxy, It is also be denoted as
Atomic Layer Deposition (ALD) or Atomic Layer Epitaxy (ALE)
Activation Energy In CVD
The CVD process requires some sort of energy input to dissociate the
precursors to form reactive intermediates that deposit on the substrate.

1)The majority of CVD processes are thermally activated by applying temperatures

typically in the range 200-2000°C.
Example .Preparation of TiB2, (melting point 3325˚C.) May be deposited by CVD at 1000˚C:-
TiCl4 + 2BCl3 + 5H2 → TiB2 + 10HCl
2) A plasma can be used as a sores of activation energy. The chemical reactions
activated by electron impact collisions and by the generation of ions and radicals.
These processes are referred to as Plasma Enhanced CVD (PECVD) or alternatively
Plasma Assisted CVD (PACVD).
3) The gas phase chemistry can also be activated by photons. Laser Enhanced CVD
(LECVD) or Photo Assisted CVD.
A plasma is any gas in which a significant percentage of the atoms or
molecules are ionized.
plasma can be artificially generated by heating a neutral gas or subjecting it to
a strong electromagnetic field.
 Chemical processes in CVD
In most, but not all, CVD processes the precursors undergo gas phase chemical reactions that result in the formation of more
reactive species. The reactions may be activated thermally or by an external source of energy, e.g. application of a plasma.

All CVD processes involve surface chemical processes and most CVD processes, with the exception of pure atomic layer
deposition (ALD) processes ((ALD) uses only surface chemical reactions to build up thin films with great precision), involve
also gas phase chemical reactions.

Thin film growth by CVD is the result of a complex sequence of chemical reactions.
 Steps in the CVD process

1- Transport of the reagents (e.g. TiCl4, BCl3, H2) in the gas phase (often with carrier gas) to the reaction zone
2- Diffusion (or convection) through the boundary layer
3- Adsorption of precursors on the substrate
4- Surface diffusion of the precursors to growth sites. Reaction without diffusion is not wanted, as this may lead to rough
growth surface.
5- Surface chemical reaction, formation of a solid film and formation of byproducts.
6- Desorption of by-products.
The ideal precursor but it is Impossible to meet all criteria
• Liquid rather than solid or gaseous
• Good volatility
• Good thermal stability in the delivery system, during evaporation and transport
• Decompose cleanly and controllably on the substrate without incorporation
• Give stable by-products which are readily removed from the reaction zone
• Readily available in consistent quality and quantity at low cost
• Non-toxic and non-pyrophoric.
 CVD Thin films applications

Many materials may be deposited using CVD and related techniques. Metals,
oxides, sulfides, nitrides, phosphides, arsenides, carbides, borides, silicides….
Etc.

Intended properties of the CVD deposited thin films

•Protection (corrosion, wear…) •Optical properties •Electronic properties

•Magnetic properties •Decoration
 CVD Thin films applications
1- Hard coatings (cutting tools etc.)
2- Functional coatings on glass, (SnO2, TiN, SiO2, TiO2) One of the most important reasons
for coating a window is to prevent heat passing through, reducing the need for cooling down
or warming up buildings, and thus reducing energy consumption.
Typically films of transparent SnO2:F (fluorine doped tin oxide thin film ) are used for this
application. The coating can also reflect some of the incoming light and for this, TiN films are
employed. These films are deposited on the glass as a final production step by an atmospheric
pressure CVD technique mounted on the float glass production line.
3- Microelectronics, It is fair to say that without CVD we would not have the electronics that
we take for granted today. All sorts of electronic devices are constructed from stacks of thin
layers with highly controlled electrical properties and CVD is often the method of choice for
depositing these thin layers.
4- Solar cells, catalysis, membranes, waveguides, mirrors, ”synthetic gold” (TiNx)
 Physical vapor deposition (PVD)

Physical vapor deposition (PVD) covers a broad class of vacuum coating

processes in which material is physically removed from a source by evaporation
or sputtering, transported through a vacuum or partial vacuum by the energy of
the vapor particles, and condensed as a film on the surfaces of appropriately
placed parts or substrates.
The substance to be evaporated is heated in a dedicated container by the
introduction of energy to a suitable temperature.
The thermally released atoms or molecules leave the surface of the evaporated
material and form a coating on the substrate.
As the process is usually conducted under High Vacuum (p < 10-5 mbar = 10-3
Pa) the coating particles basically move from the source to the substrates
(without collisions with residual gas atoms) on straight trajectories.
PVD coating is an environmentally friendly vacuum coating
process.
Due to its excellent wear and corrosion resistance, PVD is often
used to give parts enhanced performance and a brilliant decorative
finish.
PVD coating processes are common in industrial, non-industrial,
and cosmetic applications. It is a very important surface finishing
process in the modern manufacturing industry.
 Classification of Physical deposition methods
There are a variety of PVD processes which cover a
spectrum of functionally and aesthetically desirable
attributes. However, the three most commonly used forms
are thermal evaporation, sputter deposition, and arc vapor
deposition.
There are subsets of each PVD coating process, but all
achieve similar results.
1.Thermal evaporation method
This method is the one of the most well-known physical deposition methods.
The deposited material is created in a vapor form by heating bulk material in
vacuum with resistive heater.
The vapor atoms are transported through vacuum to get deposited on desired
substrate. This vapour deposition is done only at pressure less than 10 -5 torr.

Due to its simplicity, the Thermal Evaporation PVD comes with the following
applications:
Solar cells, Cell phones, Optical applications Toys, Cosmetics, Shoe heels,
Computers,
The advantages of this deposition method are it is simple and cheap with less
substrate surface damage. Excellent purity and desired thickness of the thin
films can be achieved. High deposition rate than others, No atmospheric of
the pollution overall.
The disadvantages the deposited films have poor density and adhesion. It is
limited to low melting point metals. Therefore, dielectric materials cannot be
evaporated by this method, need a water-cooling system for substrate.
2- Sputtering Deposition
A plasma at higher pressure is used to “knock” metal atoms out of a
“target”. These energetic atoms deposit on a wafer located near the
target. The higher pressure produces better step coverage due to more
random angled delivery. The excess energy of the ions also aids in
increasing the surface mobility (movement of atoms on the surface)
In this process, the sputtered high-energy ions will fly towards the
substrate ballistically and get deposited layer by layer to form the
coating.
Coating Substance converted in to Vapor by bombarding
accelerated gas atoms into coating substance .
 disadvantages
advantages *The process is
* No atmospheric
complicated.
pollution.
*The chamber also
*No heated parts.
gets coated during
*Available for
the process.
high-melting-point
*May produce
coating substance
impurities on the
materials
surface of the
substrate.
3- arc vapor deposition.
The cathodic arc is a low-voltage, high-current plasma discharge
that takes place between two metallic electrodes in vacuum.
Cathodic arc deposition or Arc-PVD is a physical vapor
deposition technique in which an electric arc is used to vaporize
material from a cathode target. The vaporized material then
condenses on a substrate, forming a thin film. The technique can
be used to deposit metallic, ceramic, and composite films. The
temperature at the cathode spot is extremely high which results in
a high velocity jet of vaporized cathode material.
The cathode spot is only active for a short period of time
An electric arc (or arc discharge) is an electrical breakdown of a gas that
produces a prolonged electrical discharge. The current through a normally
nonconductive medium such as air produces a plasma, the plasma may
produce visible light.

An electric arc between two nails

If a reactive gas is introduced during the evaporation process,
dissociation, ionization, and excitation can occur during interaction
with the ion flux, and a compound film will be deposited.
 disadvantage is its
Advantages inability to coat
• good film complex
adhesion, geometries
• excellent
stoichiometric
control,
• multilayer
compact
coating,
• uniform film,
• and low
voltage.
Cathodic arc deposition is actively used to synthesize extremely hard films to
protect the surface of cutting tools and extend their life significantly. A wide
variety of thin hard-film, Superhard coatings and nanocomposite coatings can
be synthesized by this technology including TiN, TiAlN, CrN, ZrN, AlCrTiN and
TiAlSiN.

Aluminium Titanium Nitride

(AlTiN) coated endmills using
Cathodic arc deposition technique
Titanium Nitride (TiN) coated punches
4- Electron beam evaporation method
In this method, an electron gun is used for evaporation. It consists of a heated
filament for electron emission. The filament is normally shielded to prevent any
sputtering by vapor species and gaseous ions. An electron beam is accelerated
through potential of 5 to 10 KV and focused on the material.
The temperature of the evaporated material can be raised by electron
bombardment instead of resistive heating.
Due to a higher deposition rate the process, is mostly in the following industry:
Solar panels, Semiconductor Industry,

advantages disadvantages
* the material * the filament
utilization degradation in the
efficiency is high as electron gun results
compared to other in non-uniform
deposition methods. evaporation rate
* structural and * it cannot be used
morphological to coat the inner
control of films. * surface of complex
very high geometries.
deposition rate
 5. Activated reactive evaporation (ARE) method The evaporation of a metal
occurs in the presence of a reactive gas and plasma to deposit compounds with
increased adhesion and increased deposition rates. The deposition technique
has been mainly used to deposit highly adherent films of oxides and carbides.
Advantages disadvantages
* extremely high * high substrate
deposition rates, * temperature,
variety of coating * addition of an extra
compositions, * electrode, * slightly
precise control of complicated
stoichiometry, * compared to
better adhesion and evaporation,
denser microstructure * substrate must
than direct generally be rotated
evaporation. for uniform coating.
6- Pulsed Laser Deposition
This is a very new process, and it is still in its developing phase. In this process,
the coating substance is first evaporated by a laser beam, and afterward, emitted
vapors get deposited on the substrate surface to form the coating.
The Coating Substance converted in to Vapor by bombarding high energy laser
beam into coating substance.
Advantages
•Real-time Disadvantages
thickness control •Equipment used
•No limitation in is expensive
using a coating •No effective
substance commercial
•Can be used machine yet
both with inert
and reactive
gases.
•Suitable for low
melting point
substrates such
as plastics