1. Introduction.

2. Chemical Vapour Deposition.

2.1 Low Pressure Chemical Vapour Deposition (LPCVD).
2.2 Plasma Enhanced Chemical Vapour Deposition (PECVD).

1. Introduction

Chemical deposition techniques play a very crucial role in the design and manufacture of several useful
devices. These techniques are employed to produce high quality and high-performance solid materials.
They are mainly used to produce thin films.

These techniques help in overcoming several drawbacks which we observe in physical deposition
techniques like poor conformality, low throughput, restricted directional variation and reduced
compositional control.

This field is dominated by mainly two groups:

1. The first group comprising Chemical Vapor Deposition (CVD) and Atomic Layer Deposition
(ALD). Both these techniques comprise of a process in which gas phase is used to transport
volatile molecules to the surface serving as substrate.
2. The second group having technique known as Chemical Solution Processing or Sol-Gel
Processing which uses liquid phase as the mass transfer media.

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Chemical vapor deposition process

In both the processes, the basic technique employed is the same. The final material in both the cases is
created by molecules of chemical compounds which are being served as precursors.

Precursor is one of the compounds that participate in the chemical reaction that produces another
compound. These precursors are directed to the substrate surface and been chemically modified to obtain
the desired film.

2. CHEMICAL VAPOUR DEPOSITION

In this process, the substrate (often referred to as wafer) which is placed inside a chamber is exposed to
one or more volatile precursors which get deposited on the substrate to produce the desired film. Since
there is a chemical reaction involved, so very frequently by-products are released which are removed by
gas flow through the reaction chamber.

In micro-device fabrication, CVD is widely used to deposit materials in various forms such as:
monocrystalline, polycrystalline, amorphous and epitaxial. The materials which are often deposited by
CVD are: Sulfides, Oxides, Nitrides, carbides, silicides etc.

A simple prototype thermal CVD Reactor

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Chemical vapor deposition process

TYPES OF CVD:

CVD is divided into several categories based on different criteria which are as follows:

1. On the basis of OPERATING PRESSURE:

i) Atmospheric pressure CVD (APCVD)- Deposition is done at atmospheric pressure. This
process has advantage of fast deposition at low temperature. But the major disadvantage is
low purity.
ii) Low pressure CVD (LPCVD - Reduced pressure is required for good uniformity of film
because it ensures the reduction of unwanted gas-phase reactions). The pressure ranges from

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Chemical vapor deposition process

 30 to 250 pa
iii) Ultrahigh Vacuum CVD (UHVCVD - The pressure is significantly reduced up to or less than
10−6 pa (∼ 10−8 Torr).

The CVD which is used prominently in modern world is either LPCVD or UHVCVD. The reduced
pressure in the reaction chamber during LPCVD and UHCVD processes enhances the gas diffusivity,
which reduces the unwanted gas phase reactions and improving coating uniformity.

2. On the basis of Physical Characteristics of Vapour.

i) Aerosol assisted CVD (AACVD) – In this the precursors are transported to the substrate by
the means of liquid/gas aerosol, which is generated with the aid of ultrasonic treatment. This
technique is employed when we have non-volatile precursors.
ii) Direct liquid injection CVD (DLICVD) – The precursor in this CVD is in liquid form or solid
dissolved in suitable solvent. This liquid precursor is injected into the vaporization chamber
directed towards the injectors. The precursor vapors in the process are transported to the
substrate just as in the case of classical CVD. This technique is being used in the case of solid
or liquid precursors. This technique is also an aid in achieving high growth rates due to perfect
control of precursor flow (control of the liquid flow). DLICVD also has advantage of
3. On Accurate
the basis control of doping
of Plasma level
Methods.
i) Plasma Enhanced CVD (PECVD) – This process utilizes plasma to enhance reaction rate of
the precursors. This allows the deposition at lower temperature, which is a very critical
parameter in the manufacture of semiconductors. Lower temperatures also inhibit the
deposition of organic coatings such as plasma polymers, which have been used for
nanoparticle surface fictionalization.
ii) Microwave plasma assisted CVD (MPCVD) - This process utilizes a microwave plasma
source.
iii) Remote plasma-enhanced CVD (RPECVD) – this is similar to PECVD except that in this
wafer (substrate) is not directly placed in the plasma discharge region. This has a benefit that
we can reduce the processing temperature down to room temperature.

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There are several other kinds of CVD processes such as Atomic layer CVD, Combustion CVD, Hot
filament CVD, Hybrid Physical-CVD, Metal organic-CVD, rapid thermal-CVD, vapor phase epitaxy
and Photo-Initiated CVD.

The most frequently used CVD techniques in the modern times are LPCVD and PECVD. So let us
learn about them more in the forthcoming sections.

2.1 Low pressure chemical vapor deposition (LPCVD)

It is that chemical vapor deposition technique in which heat is used to initiate the reaction of precursor
gas onto the substrate (solid). In this deposition of thin films on semiconductor substrate occurs usually
ranging from a few nanometers to many micrometers.

The reaction occurring is responsible for the formation of solid phase material. Low pressure ensures
that no unwanted gas phase reaction occurs and also the uniformity across the substrate enhances.

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Mode of Operation – It can be performed in either hot or cold walled quartz tube reactor.
Hot walls operation has an advantage that it allows batch processing and hence a better throughput.
They also increase thermal uniformity and hence as a result, uniform films are obtained.

But it has a disadvantage also. In this process, the deposition also occurs on the hot furnace walls which
bound us to frequently clean the chamber and to replace the tube so as to avoid particle contamination in
the subsequent deposition. Cold walled reactors have an advantage on this part because they are low
maintenance as there is no deposition on the chamber walls.

In LPCVD, tube is evacuated to low pressures, in the range of 10 m Torr to 1 Torr. Now when the
tube is under vacuum, it is heated up to the required deposition temperature (which is the temperature at
which the precursor gas starts decomposing).

Temperatures which are attained in LPCVD generally lie in the range 425-900°C depending upon the
process and the reactive gases being used. After attaining the desired temperature, gas in inserted into
the tube. This gas then diffuses in the tube and reacts with the surface of the substrate which leads to
formation of the solid phase material. Excess gas if any is then pumped out of the tube and goes through
the abatement system.

The main reason for using LPCVD in place of APCVD is the ratio of the mass transport velocity and the
velocity of reaction on the surface. It is often observed that, LPCVD films are more uniform, lower
in defects and exhibit better step coverage than the films produced by conventional PECVD and
PVD techniques.

During APCVD the ratio of the mass transport velocity and the velocity of reaction on the surface is
close to one as the two velocities are of the same order of magnitude. The velocity of the mass transport
depends mainly on the reactant concentration, diffusion, and thickness of the border layer.

When the pressure is lowered during LPCVD, the diffusion of the gas decreases proportionally to the
reciprocal of the pressure. The pressure for LPCVD is usually around 10-1000 Pa while standard
atmospheric pressure is 101,325 Pa. If the pressure is lowered from atmospheric pressure to about 100
Pa the diffusion will decrease by almost 1000. This means that the velocity of mass transport will
decrease meaning the substrates can approach more closely and the deposited films show better

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uniformity and homogeneity.

Despite of having so many advantages, it suffers from a disadvantage also which is that it requires higher
temperatures. Requirement of high temperature limits the types of substrate and other materials which
can be present on the samples.

APPLICATIONS – LPCVD is mostly employed to deposit polysilicon (used for gate contacts),
silicon nitride and silicon dioxide (used for isolation). Most LPCVD films are with good conformal
step coverage and offer good sidewall protection.

2.2 Plasma enhanced chemical vapor deposition (PECVD)

This is the CVD process which uses plasma (cold plasma) to deposit thin films from a gas state to a
solid state on a substrate. The reaction involved in this process occurs after the creation of plasma of
the reacting gases. This plasma is created by application of RF (AC) frequency or DC discharge
between two electrodes.

The space between the electrodes is filled with the reacting gases. Through this process, we can deposit
films on substrates at lower temperatures than that of standard CVD.

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UNDERLYING PROCESS – Plasma is that state of gas in which a significant percentage of atoms or
molecules are ionized. Plasmas with low fractional ionization are of great use in the material processing
because electrons in such plasma are very light as compared to atoms and molecules such that the energy
exchange between the electron and the neutral gas being used for the creation of plasma is very
insignificant.

The plasma used for processing is operated at pressures between millitorr to few torr. Since the electrons
are very light so they could be maintained at a very high equivalent temperatures (tens of thousands of
kelvins) equivalent to several electron volts average energy whereas the neutral atoms remain at the
ambient temperature. These highly energetic electrons are efficient to induce many processes that would
otherwise be very difficult to process at low temperatures, such as dissociation of precursor molecules
and the creation of huge amount of free radicals.

Another benefit of deposition within a discharge arises from the fact that electrons are more mobile than
ions. Due to this, plasma becomes the most positive among the things it is in contact with. The difference
of the voltage between plasma and the objects in its contacts generally occurs across a thin sheath region.
Ionized atoms or molecules diffuse to the edge of the sheath region. They feel an electrostatic force and
are accelerated towards the neighboring surface.

Thus, all the surfaces which are exposed to the plasma get energetic ion bombardment. The potential
across the sheath that surrounds an electrically-isolated object is around 10–20 V, but much higher sheath
potentials can be achieved by adjustments in reactor geometry and configuration. Thus, films can be
exposed to energetic ion bombardment during deposition. This bombardment often leads to increase in
density of the film, and help to remove contamination thus improving film's electrical and mechanical
properties.

When high-density plasma is used, the ion density is high enough such that significant sputtering of the
deposited film occurs; this sputtering can be used to help in making the film plain and fill troughs or
holes.

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There are two parallel electrodes in the system – a grounded electrode and an RF-energized electrode.
This capacitive coupling between the electrodes excites the reactant gases into plasma, which then
induces a chemical reaction and results in the reaction product which is then deposited at the substrate.

The substrate is placed at the grounded electrode is generally heated to 250° C to 350° C, depending on
the film that needs to be deposited. In comparison CVD requires 600° C to 800° C. The lower temperature
requirement is very essential in some cases where high temperatures such as in CVD may damage the
device being fabricated.

APPLICATIONS – It has many important applications in material deposition. It has been used
commercially to deposit following films:

• Oxides and Nitrides of Silicon (SiOx, SiNx and SiOxNy) deposition for a wide range
of applications including photonics structures, passivation, hard mask, etc.

• Amorphous silicon (a-Si:H)

• Tetraethyl orthosilicate (TEOS SiO2) with conformal step coverage, or void-free good step
coverage

• Silicon Carbide (SiC)

• Diamond-like carbon (DLC)

ADVANTAGES:
• Low operating temperature.
• Uniform coating of different shapes.
• Good step coverage.
• High packing density.
• Film characteristics as a function of depth.
• Less stress.
DISADVANTAGES:
• Precursors are toxic and so are the byproducts.
• Equipment is not economical.

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Chemical vapor deposition process

 • Capacity is limited.
• Contamination occurs from precursor and carrier molecules.
• Stoichiometry is hard to obtain.

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Chemical vapor deposition process