Part-II

Thin film deposition techniques

 Chemical vapour deposition (CVD)
Chemical vapor deposition (CVD) is a chemical process used to produce high-purity, high-
performance solid materials. The process is often used in the semiconductor industry to
produce thin films. In a typical CVD process, the wafer (substrate) is exposed to one or more
volatile precursors, which react and/or decompose on the substrate surface to produce the
desired deposit. Frequently, volatile by-products are also produced, which are removed by gas
flow through the reaction chamber.
Microfabrication processes widely use CVD to deposit materials in various forms, including:
polycrystalline, amorphous, and epitaxial. These materials include: silicon, carbon fiber,
carbon nanofibers, filaments, carbon nanotubes, SiO 2, silicon-germanium, tungsten, silicon
carbide, silicon nitride, silicon oxynitride, titanium nitride, and various high-k dielectrics. The
CVD process is also used to produce synthetic diamonds.
 Fig. 2. Thermal CVD process.

Fig. 1. The CVD process. Fig. 3. Plasma assisted CVD process (PECVD).
 Types of CVD
A number of forms of CVD are in wide use and are frequently referenced in the literature. These
processes differ in the means by which chemical reactions are initiated (e.g., activation process)
and process conditions.
 Classified by operating pressure :
Atmospheric pressure CVD (APCVD)
Low-pressure CVD (LPCVD) - CVD processes at sub-atmospheric pressures. Reduced
pressures tend to reduce unwanted gas-phase reactions and improve film uniformity across

the wafer.
Ultrahigh vacuum CVD (UHVCVD) - CVD processes at a very low pressure, typically below 10 -6

Pa (~10-8 torr). Most modern CVD processes are either LPCVD or UHVCVD.
 Classified by physical characteristics of vapor :
Aerosol assisted CVD (AACVD) - A CVD process in which the precursors are transported to
the substrate by means of a liquid/gas aerosol, which can be generated ultrasonically. This
technique is suitable for use with non-volatile precursors.
Direct liquid injection CVD (DLICVD) - A CVD process in which the precursors are in liquid
form (liquid or solid dissolved in a convenient solvent). Liquid solutions are injected in a
vaporization chamber towards injectors (typically car injectors). Then the precursor vapors
are transported to the substrate as in classical CVD process. This technique is suitable for
use on liquid or solid precursors. High growth rates can be reached using this technique.
 Plasma methods :
Microwave plasma-assisted CVD (MPCVD)
Plasma-Enhanced CVD (PECVD) - CVD processes that utilize plasma to enhance chemical
 Atomic layer CVD (ALCVD) – Deposits successive layers of different substances to produce
layered, crystalline films.
 Hot wire CVD (HWCVD) - also known as catalytic CVD (Cat-CVD) or hot filament CVD
(HFCVD). Uses a hot filament to chemically decompose the source gases.
 Metalorganic chemical vapor deposition (MOCVD) - CVD processes based on metalorganic
precursors.
 Hybrid Physical-Chemical Vapor Deposition (HPCVD) - Vapor deposition processes that
involve both chemical decomposition of precursor gas and vaporization of a solid source.
 Rapid thermal CVD (RTCVD) - CVD processes that use heating lamps or other methods to
rapidly heat the wafer substrate. Heating only the substrate rather than the gas or chamber
walls helps reduce unwanted gas phase reactions that can lead to particle formation.
 Typical examples of CVD reactions used in IC fabrications

Polysilicon :
Polycrystalline silicon is deposited from silane (SiH 4), using the following reaction :
SiH4 → Si + 2H2
This reaction is usually performed in LPCVD systems, with either pure silane feedstock, or a solution
of silane with 70-80% nitrogen. Temperatures between 600 and 650 °C and pressures between 25 and
150 Pa yield a growth rate between 10 and 20 nm per minute. An alternative process uses a hydrogen
based solution. The hydrogen reduces the growth rate, but the temperature is raised to 850 or even
1050 °C to compensate.
Polysilicon may be grown directly with doping, if gases such as phosphine, arsine or diborane are
added to the CVD chamber. Diborane increases the growth rate, but arsine and phosphine decrease
it.
Silicon dioxide :
Silicon dioxide may be deposited by several different processes. Common source gases include silane
and oxygen, dichlorosilane (SiCl2H2) and nitrous oxide (N2O), or tetraethylorthosilicate (TEOS;
Si(OC2H5)4). The reactions are as follows :
SiH4 + O2 → SiO2 + 2 H2
SiCl2H2 + 2 N2O → SiO2 + 2 N2 + 2 HCl
Si(OC2H5)4 → SiO2 + byproducts
Silicon nitride :
Silicon nitride is often used as an insulator and chemical barrier in manufacturing ICs. The following
two reactions deposit nitride from the gas phase :
3 SiH4 + 4 NH3 → Si3N4 + 12 H2
3 SiCl2H2 + 4 NH3 → Si3N4 + 6 HCl + 6 H2

Metals :
CVD processes for molybdenum, tantalum, titanium, nickel, and tungsten are widely used. These
metals can form useful silicides when deposited onto silicon. Mo, Ta and Ti are deposited by
LPCVD, from their pentachlorides. Nickel, molybdenum, and tungsten can be deposited at low
temperatures from their carbonyl precursors. In general, for an arbitrary metal M, the reaction is as
follows :
2 MCl5 + 5 H2 → 2 M + 10 HCl
The usual source for tungsten is tungsten hexafluoride, which may be deposited in two ways :
WF6 → W + 3 F2
WF6 + 3 H2 → W + 6 HF
 Metalorganic chemical vapour deposition (MOCVD)
Metalorganic vapour phase epitaxy (MOVPE) is a chemical vapour deposition method of epitaxial
growth of materials, especially compound semiconductors from the surface reaction of organic
compounds or metalorganics and metal hydrides containing the required chemical elements.
For example, indium phosphide could be grown in a reactor on a substrate by introducing
Trimethylindium ((CH3)3In) and phosphine (PH3). Alternative names for this process include
organometallic vapour phase epitaxy (OMVPE), metalorganic chemical vapour deposition (MOCVD)
and organometallic chemical vapour deposition (OMCVD).
Formation of the epitaxial layer occurs by final pyrolisis of the constituent chemicals at the
substrate surface. In contrast to molecular beam epitaxy (MBE) the growth of crystals is by
chemical reaction and not physical deposition. This takes place not in a vacuum, but from the gas
phase at moderate pressures (2 to 100 kPa). As such this technique is preferred for the formation of
devices incorporating thermodynamically metastable alloys. It has become the dominant process
for the manufacture of laser diodes, solar cells, and LEDs.
 Liquid Phase Epitaxy (LPE)
Liquid phase epitaxy (LPE) is a method to grow semiconductor crystal layers from the
melt on solid substrates. This happens at temperatures well below the melting point of
the deposited semiconductor. The semiconductor is dissolved in the melt of another
material. At conditions that are close to the equilibrium between dissolution and
deposition, the deposition of the semiconductor crystal on the substrate is slow and
uniform. The equilibrium conditions depend very much on the temperature and on the
concentration of the dissolved semiconductor in the melt. The growth of the layer from
the liquid phase can be controlled by a forced cooling of the melt. Impurity introduction
can be strongly reduced. Doping can be achieved by the addition of dopants.
The method is mainly used for the growth of compound semiconductors. Very thin,
uniform and high quality layers can be produced. A typical example for the liquid phase
epitaxy method is the growth of ternary and quaternary III-V compounds on
Galliumarsenide (GaAs) substrates. As a solvent quite often Gallium is used in this case.
Another frequently used substrate is Indiumphosphide (InP). However, other substrates
like glass or ceramic can also be applied for special applications.
To facilitate nucleation, and to avoid tension in the grown layer the thermal expansion
coefficient of substrate and grown layer should be similar.
In the case of a horizontal tool for liquid phase epitaxy the melt or the melts are brought in contact
with the substrate (s) by a sliding boat system. When the dedicated process is finished the next
melt can be brought in contact with the next substrate.
This way, it is possible to grow multi-layer stacks in an easy way. Depending on the set-up of the
system one or several wafer can be processed at the same time. The melt volume to substrate
surface area ratio is small, and the melt needs to be refreshed after each growth experiment.
A vertical system can be used in combination with a dipping system for the liquid phase epitaxy
growth. The samples are lowered into the melt with the aid of a pull-rod.
In this system the melt volume to substrate surface area is much higher, giving the opportunity to
grow thicker layers at a relatively high rate.
 Molecular beam epitaxy (MBE)
Molecular beam epitaxy takes place in high vacuum or ultra high vacuum (10 −8 Pa). The most
important aspect of MBE is the slow deposition rate (typically less than 1000 nm per hour), which
allows the films to grow epitaxially. The slow deposition rates require proportionally better vacuum
to achieve the same impurity levels as other deposition techniques.

In solid-source MBE, ultra-pure elements such as gallium and arsenic are heated in separate quasi-
knudsen effusion cells until they begin to slowly sublimate. The gaseous elements then condense on
the wafer, where they may react with each other. In the example of gallium and arsenic, single-crystal
gallium arsenide is formed. The term "beam" means that evaporated atoms do not interact with each
other or vacuum chamber gases until they reach the wafer, due to the long mean free paths of the
atoms.
During operation, RHEED (Reflection High Energy Electron Diffraction) is often used for
monitoring the growth of the crystal layers. A computer controls shutters in front of each
furnace, allowing precise control of the thickness of each layer, down to a single layer of
atoms. Intricate structures of layers of different materials may be fabricated this way. Such
control has allowed the development of structures where the electrons can be confined in
space, giving quantum wells or even quantum dots. Such layers are now a critical part of
many modern semiconductor devices, including semiconductor lasers and light-emitting
diodes.
In systems where the substrate needs to be cooled, the ultra-high vacuum environment within
the growth chamber is maintained by a system of cryopumps, and cryopanels, chilled using
liquid nitrogen or cold nitrogen gas to a temperature close to 77 K (−196°C). Cryogenic
temperatures act as a sink for impurities in the vacuum, so vacuum levels need to be several
orders of magnitude better to deposit films under these conditions. In other systems, the
wafers on which the crystals are grown may be mounted on a rotating platter which can be
heated to several hundred degrees Celsius during operation.
Molecular beam epitaxy is also used for the deposition of some types of organic
semiconductors. In this case, molecules, rather than atoms, are evaporated and deposited
onto the wafer. Other variations include gas-source MBE, which resembles CVD.
 Asaro-Tiller-Grinfeld (ATG) instability
The ATG (Asaro-Tiller-Grinfeld) instability, also known as the Grinfeld instability, is an
elastic instability often encountered in thin film technology. If there is a mismatch
between the lattice sizes of the growing film and the supporting crystal, elastic energy
will be accumulated in the growing film. At some critical height, the free energy of the
film can be lowered if the film breaks into isolated islands, where the tension can be
relaxed laterally. The critical height depends on Young moduli, mismatch size, and
surface tensions.
Some applications for this instability have been researched, such as the self-assembly of
quantum dots. This community uses the name of Stranski-Krastanov for ATG.
 Physical deposition techniques
Physical deposition techniques uses mechanical or thermodynamic means to produce a
thin film of solid. An everyday example is the formation of frost. Since most engineering
materials are held together by relatively high energies, and chemical reactions are not
used to store these energies, commercial physical deposition systems tend to require a
low-pressure vapor environment to function properly; most can be classified as physical
vapor deposition (PVD).
PVD is a variety of vacuum deposition and is a general term used to describe any of a
variety of methods to deposit thin films by the condensation of a vaporized form of the
material onto various surfaces (e.g., onto semiconductor wafers). The coating method
involves purely physical processes such as high temperature vacuum evaporation or
plasma sputter bombardment rather than involving a chemical reaction at the surface to
be coated as in chemical vapor deposition.
The material to be deposited is placed in an energetic, entropic environment, so that
particles of material escape its surface. Facing this source is a cooler surface which
draws energy from these particles as they arrive, allowing them to form a solid layer. The
whole system is kept in a vacuum deposition chamber, to allow the particles to travel as
freely as possible. Since particles tend to follow a straight path, films deposited by
physical means are commonly directional, rather than conformal.
Examples of PVD include : Thermal evaporation, electron beam evaporation, sputtering,
pulsed laser deposition, cathodic arc deposition, etc.
 Thermal evaporation technique
In the thermal evaporation technique, an electric resistance heater is used to melt the material and raises its
vapor pressure to a useful range. This is done in a high vacuum, both to allow the vapor to reach the
substrate without reacting with or scattering against other gas-phase atoms in the chamber, and reduce the
incorporation of impurities from the residual gas in the vacuum chamber. Obviously, only materials with a
much higher vapor pressure than the heating element can be deposited without contamination of the film.
MBE is a particular sophisticated form of thermal evaporation.
The material is heated until fusion by means of an electrical current passing through a filament or metal plate
where the material is deposited (Joule effect). The evaporated material is then condensed on the substrate.
Other ways of heating are used, such as a RF coil surrounding a graphite or BN crucible, where the material
to be evaporated is fused. The assembly of the technique is simple and results appropriate for depositing
metals and some compounds with low fusion temperature (Al, Ag, Au, SiO, etc.).
Typical metals used as heating resistance are tantalum (Ta), Molybdenum (Mo) and wolfram (W), with vapor
pressure practically zero at the evaporation temperature (Tevap = 1000-2000°C).
 Electron beam evaporation technique (EB-PVD)
This technique is based in the heat produced by high energy electron beam bombardment on the
material to be deposited. The electron beam is generated by an electron gun, which uses the thermo
ionic emission of electrons produced by an incandescent filament (cathode). Emitted electrons are
accelerated towards an anode by a high difference of potential (kilovolts). The crucible itself or a
near perforated disc can act as the anode. A magnetic field is applied to bend the electron trajectory,
allowing the electron gun to be positioned below the evaporation line.
As electrons can be focused, it is possible to obtain a very localized heating on the material to
evaporate, with a high density of evaporation power (several kW). This allows to control the
evaporation rate, from low to very high values, and best of all, the chance of depositing materials
with high melting point (W, Ta, C, etc.). Cooling the crucible avoids contamination problems from
heating and degasification. Typical deposition rates for electron beam evaporation range from 1 to 10
nanometers per second.
 Sputtering techniques
Sputtering relies on a plasma (usually a noble gas, such as Ar) to knock material from a "target" a
few atoms at a time. The target can be kept at a relatively low temperature, since the process is not
one of evaporation, making this one of the most flexible deposition techniques. It is especially useful
for compounds or mixtures, where different components would otherwise tend to evaporate at
different rates.
Sputtering step coverage is more or less conformal. It is also widely used in the optical media. The
manufacturing of all formats of CD, DVD, etc., are basically done with the help of this technique. It is
a fast technique and also it provides a good thickness control.
The main principle is to build a vaccum chamber and fill with Ar. By applying a high voltage, the Ar
will arc to plasma state. The argon ions (Ar+) will move towards the cathode with high speed and
sputter the target material (the target is used as cathode). The target atom or molecules will hit the
substrate surface and condense as a thin film.
Instead of heat melting in evaporation method, the plasma (Ar+) ion hit and sputter the target is the
main mechanism in plasma sputtering method. The target atom is knocked out by Ar+ ion, the knock
force is so intense that it can accelerate target atom to a high speed. With such velocity, the target
atom can hit and attach to substrate surface deeply.
DC sputtering (Planar diode sputtering) : Using target as cathode and substrate as anode, pump the
vaccum to 10-3 Pa, fill argon gas, apply ~1000 V Voltage. The ions in plasma will be accelerated
towards the cathode, hit the target and transfer the energy in sputtering the target to substrate
surface. DC supttering use target as a cathode. It must be a conductive material (metal). It can't
sputter dielectric material target.
RF sputtering : In DC systems, positive charge will accumulate on the cathode (target) and need 10 12
volts to sputter insulators. But such high voltage will make arcing and harm the target source and
produced film. It was improved by Wehner in 1955. An alternative voltage in Radio Frequency
13.5MHz was applied in DC system. With alternative characteristics, the positive charge will stay in
the plasma zone and not accumulate near the cathode. The cathode can sustain a high voltage
difference and continue the sputtering work.

Dual cathode sputtering : To improve the speed of deposition rate, dual cathodes are used. A ~40
KHz frequency alternative voltage is applied to the dual cathodes. It will steadily change the positive
and negative poles in the cathodes. This alternative voltage in kept much lower than the anode
voltage. The alternative current will neutralize the accumulated charges in target source.
Triode sputtering : It increases the quantity of Ar+ hitting the target which effectively increases the
sputtering rate.
Magnetron sputtering : By adding a magnetic field in the system, the electron will move in spiral
following the magnetic lineation. This will hugely increase the ionization density of argon gas and
probability of collision. Therefore, the deposition rate will be increased. This system can also be
applied to DC, RF, Dual cathode Sputtering methods. It can also be applied to some substrates which
can't stand for high working temperature. Most important of all, it can join into continuous
production line.
 Linear magnetron sputtering Off-axis magnetron sputtering with RF system

Ion beam sputtering (IBS) : This method is newest developed and may be the most
important for high class optical filters. It has an isolated ion source in a high vacuum
chamber. The ion particles knock out the atom of target and the target atoms pass
through the vacuum space and deposit on substrate surface. The ions are much heavier
compared to the target atoms. This knock will be a powerful method and can transfer a
huge kinetic energy to target atom particle. In this process high class laser mirrors and
filters used in Gyro and Laser Interferometer Gravitational Wave Observatory (LIGO) can
be prepared.
 Pulsed laser deposition (PLD) techniques
PLD systems work by an ablation process. Pulses of focused laser light vaporize the surface of the
target material and convert it to plasma; this plasma usually reverts to a gas before it reaches the
substrate.
 Reactive sputtering
In reactive sputtering, a small amount of some non-noble gas such as oxygen or nitrogen is mixed
with the plasma-forming gas. After the material is sputtered from the target, it reacts with this gas, so
that the deposited film is a different material, i.e. an oxide or nitride of the target material.
In a perfect world the reactive gas would react only with the growing film to make a thin film of the
required compound. Unfortunately the reactions occur with the sputter target surface as well. This
'target poisoning' complicates reactive sputtering and reduces the thin film growth rate.

This means that we can get into a positive feedback loop, where poisoning of the sputter target
reduces the thin film growth rate, so uses less reactive gas, and so leads to more target poisoning.
This positive feedback is seen as 'target hysteresis' - sudden jumps in the thin film deposition rate,
target voltage or oxygen pressure. To successfully make compound thin films by reactive sputtering
we must stay away from these sudden jumps in the process. Best performance is achieved by
careful design of the system furniture, the pumping system, the magnetron and the gas delivery. The
target hysteresis can be completely eliminated by the use of a feedback system controlling the
reactive gas flow, the control signal can come from emission lines from the plasma, oxygen pressure
measurements or target voltage.
 Cathode arc deposition (arc-PVD)
Arc-PVD is a kind of ion beam deposition technique where an electrical arc is created that literally
blasts ions from the cathode. The arc has an extremely high power density resulting in a high level of
ionization (30-100%), multiply charged ions, neutral particles, clusters and macro-particles (droplets).
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.
The arc evaporation process begins with the striking of a high current, low voltage arc on the surface
of a cathode (known as the target) that gives rise to a small (usually a few micrometers wide), highly
energetic emitting area known as a cathode spot. The localized temperature at the cathode spot is
extremely high (around 15000 °C), which results in a high velocity (10 km/s) jet of vapourised
cathode material, leaving a crater behind on the cathode surface. The cathode spot is only active for
a short period of time, then it self-extinguishes and re-ignites in a new area close to the previous
crater. This behaviour causes the apparent motion of the arc.
As the arc is basically a current carrying conductor it can be influenced by the application of an
electromagnetic field, which in practice is used to rapidly move the arc over the entire surface of the
target, so that the total surface is eroded over time.
Cathodic arc deposition is actively used to synthesize extremely hard film to protect the surface of
cutting tools and extend their life significantly. A wide variety of thin hard-film and nanocomposite
coatings can be synthesized by this technology including TiN, TiAlN, CrN, ZrN, and TiAlSiN.
This is also used quite extensively particularly for carbon ion deposition to create diamond-like
carbon films. Because the ions are blasted from the surface ballistically, it is common for not only
single atoms, but larger clusters of atoms to be ejected. Thus, this kind of system requires a filter to
remove atom clusters from the beam before deposition. The DLC film from filtered-arc contains
extremely high percentage of sp3 diamond which is known as tetrahedral amorphous carbon, or ta-C.
 Electron beam induced deposition (EBID)
Electron beam-induced deposition (EBID) is a process of decomposing gaseous molecules by
electron beam leading to deposition of non-volatile fragments onto a nearby substrate. The electron
beam is usually provided by a scanning electron microscope that results in high spatial accuracy
(below one nanometer) and possibility to produce free-standing, three-dimensional structures.

Focused electron beam of SEM or STEM is commonly used. Focused ion beam can be applied
instead, but then the process is called ion beam-induced deposition (IBID). The precursor material is
gas, liquid or solid. Liquid or solids are gasified prior to deposition, usually through vaporization or
sublimation, and introduced, at accurately controlled rate, into the high-vacuum chamber of electron
microscope. Alternatively, solid precursor is sublimated by the electron beam itself.
When deposition occurs at high temperature or involves corrosive gases, specially designed
deposition chamber is used; it is isolated from the microscope, and the beam is introduced into it
through a micrometer-sized orifice. Small orifice size maintains differential pressure in the
microscope (vacuum) and deposition chamber (no vacuum). Such deposition mode has been used
for EBID of diamond.
The electron beam is scanned over desired shape resulting in deposition of material. The scanning is usually
computer controlled. The deposition rate depends on the partial pressure and is of the order 10 nm/s.
SEM or STEM electrons have energy too high (typically between 10 and 300 keV) to efficiently break
molecular bonds. Therefore decomposition occurs via a two-step process: any materials (substrate, holders
or the material that has already been deposited) near the deposition spot absorb primary electrons and re-
emit secondary electrons having a wide spectrum of energies (of the order 1 keV) and angles. Secondary
electrons decompose the precursor molecules.
Primary STEM electrons can be focused into spots as small as ~0.045 nm. However, the smallest structures
deposited so far by EBID are dots of ~0.7 nm diameter. The reason for reduced resolution is wide angular
range of secondary electrons, and there is no straightforward way to overcome this problem.
The range of materials deposited by EBID currently includes Al, Au, amorphous carbon, diamond, Co, Cr, Cu,
Fe, GaAs, GaN, Ge, Mo, Nb, Ni, Os, Pd, Pt, Rh, Ru, Re, Si, Si3N4, SiOx, TiOx, W, and is being expanded. The
limiting factor is availability of appropriate precursors, gaseous or having low sublimation temperature.
The most popular precursors for deposition of elemental solids are metal carbonyls of Me(CO)x structure or
metallocenes. They are easily available, but produce carbon contamination. Metal-halogen complexes (WF6,
etc.) result in cleaner deposition, but they are toxic and corrosive. Compound materials are deposited from
specially crafted, exotic gases, e.g. D2GaN3 for GaN.
Advantages :
 Deposition occurs in high-vacuum chamber of electron microscope and therefore is rather clean.
 Size of the produced structures and accuracy of deposition are unprecedented.
 The deposited material can be characterized using the electron microscopy techniques (TEM, EELS, EDS,
electron diffraction) during or right after deposition. In situ electrical and optical characterization is also
possible.
Disadvantages :
Complexity of the setup and process limits mass production.
Nanostructures of virtually any 3-dimensional shape can be deposited using computer-controlled
scanning of electron beam. Only the starting point has to be attached to the substrate, the rest of the
structure can be free standing. The achieved shapes and devices are remarkable :
World smallest magnet
Fractal nanotrees
Nanoloops (potential nanoSQUID device)
Superconducting nanowires

Letter Φ deposited from W(CO)6 by EBID

 Ion beam induced deposition (IBID)
Ion beam-induced deposition (IBID) is very similar to EBID with the major difference that focused ion
beam, usually 30 keV Ga+, is used instead of the electron beam. In both techniques, it is not the
primary beam, but secondary electrons which cause the deposition. IBID has the following
disadvantages as compared to EBID:
Angular spread of secondary electrons is larger in IBID thus resulting in lower spatial resolution.
Ga+ ions introduce additional contamination and radiation damage to the deposited structure, which
is important for electronic applications.
Deposition occurs in a focused ion beam (FIB) setup, which strongly limits characterization of the
deposit during or right after the deposition. Only SEM-like imaging using secondary electrons is
possible, and even that imaging is restricted to short observations due to sample damaging by the
Ga+ beam. The use of a dual beam instrument, that combines a FIB and an SEM in one, circumvents
this limitation.
The advantages of IBID are:
Much higher deposition rate
Higher purities.