LECTURE 15-1

Synthesis and preparation of nanomaterials

(crystalline and thinfilm)
Sol – Gel method, Chemical Vapour Deposition,
Physical Vapour Deposition

Maj Md. Ashrafuzzaman, Ph.D

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Material Processing by Sol-Gel Method
Introduction

The sol-gel process is very long known since the late 1800s. The versatility
of the technique has been rediscovered in the early 1970s when glasses
where produced without high temperature melting processes.
This made possible the organic modification of silicon compounds
(ORMOSIL), which cannot withstand high temperatures.
Sol-gel is a chemical solution process used to make ceramic and glass
materials in the form of thin films, fibers , or powders .
A sol is a colloidal (the dispersed phase is so small that gravitational forces
do not exist; only Van der Waals forces and surface charges are present) or
molecular suspension of solid particles of ions in a solvent.
A gel is a semi-rigid mass that forms when the solvent from the sol begins to
evaporate and the particles or ions left behind begin to join together in a
continuous network

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Typical precursors are metal alkoxides and metal chlorides, which
undergo hydrolysis
(Hydrolysis is a chemical reaction or process in which a
chemical compound is broken down by reaction with water) and
polycondensation reactions.
(A chemical reaction in which two or more molecules combine upon
the separation of water or some other simple substance) to form a
colloid, a system composed of solid particles (size ranging from 1 nm
to 1 μm) dispersed in a solvent.
The sol evolves then towards the formation of an inorganic network
containing a liquid phase (gel).
Formation of a metal oxide involves connecting the metal centers with
oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating
metal-oxo or metal-hydroxo polymers in solution.
The drying process serves to remove the liquid phase from the gel
thus forming a porous material, then a thermal treatment (firing) may
be performed in order to favor further polycondensation and enhance
mechanical properties.

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 The precursor sol can be either deposited on a substrate to form a film
(e.g. by dip-coating or spin-coating), cast into a suitable container with
the desired shape
(e.g. to obtain a monolithic ceramics, glasses, fibers, membranes,
aerogels), or used to synthesize powders (e.g. microspheres,
nanospheres).

In essence, the sol-gel process usually consists of 4 steps:

(1) The desired colloidal particles once dispersed in a liquid to form a
sol.
(2) The deposition of sol solution produces the coatings on the
substrates by spraying, dipping or spinning.
(3) The particles in sol are polymerized through the removal of the
stabilizing components and produce a gel in a state of a continuous
network.
(4) The final heat treatments pyrolyze the remaining organic or
inorganic components and form an amorphous or crystalline coating.

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The sol-gel approach is interesting in that it is a cheap and
low-temperature technique that allows for the fine control
on the product’s chemical composition,
as even small quantities of dopants, such as organic dyes
and rare earth metals, can be introduced in the sol and end
up in the final product finely dispersed.
An overview of the sol-gel process is presented in a simple
graphic work below.

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Sol-Gel process overview

UNIT IV LECTURE 3 6
Advantages of Sol-Gel Technique:
Can produce thin bond-coating to provide excellent adhesion
between the metallic substrate and the top coat.
Can produce thick coating to provide corrosion protection
performance.
Can easily shape materials into complex geometries in a gel state.
Can produce high purity products because the organo-metallic
precursor of the desired ceramic oxides can be mixed, dissolved in
a specified solvent and hydrolyzed into a sol, and subsequently a
gel, the composition can be highly controllable.
Can have low temperature sintering capability, usually 200-600°C.
Can provide a simple, economic and effective method to produce
high quality coatings.

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Applications
It can be used in ceramics manufacturing processes, as an
investment casting material, or as a means of producing very
thin films of metal oxides for various purposes.
Sol-gel derived materials have diverse applications in optics,
electronics, energy, space, (bio)sensors, medicine (e.g. controlled
drug release) and separation (e.g. chromatography) technology.
One of the more important applications of sol-gel processing is to
carry out zeolite synthesis.
Other elements (metals, metal oxides) can be easily incorporated
into the final product and the silicalite sol formed by this method is
very stable.
Other products fabricated with this process include various ceramic
membranes for microfiltration, ultrafiltration, nanofiltration,
pervaporation and reverse osmosis.

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Chemical Vapour Deposition
Introduction
Chemical vapour deposition or CVD is a generic name for a
group of processes that involve depositing a solid material from
a gaseous phase.
Microfabrication processes widely use CVD to deposit materials
in various forms, including: monocrystalline, polycrystalline,
amorphous, and epitaxial.
These materials include: silicon, carbon fiber, carbon nanofibers,
filaments, carbon nanotubes, SiO2, silicon-germanium, tungsten,
silicon carbide, silicon nitride, silicon oxynitride and titanium
nitride.
CVD process is also used to produce synthetic diamonds.

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Working Concept

• Chemical vapor deposition (CVD) results from the chemical reaction

of gaseous precursor(s) at a heated substrate to yield a fully dense
deposit.
• Thermodynamics and kinetics drive both precursor generation and
decomposition.
• Control of thermodynamics and kinetics through temperature,
pressure, and concentrations yields the desired deposit.
• A simplified concept diagram is shown as Fig
• Metal deposition
metal halide (g)  →  metal(s) + byproduct (g)
• Ceramic deposition
metal halide (g) + oxygen/carbon/nitrogen/boron source (g) →
ceramic(s) + byproduct (g)
g- gas; s-solid

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CVD REACTION

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A basic CVD process consists of the following steps: 
a predefined mix of reactant gases and diluent inert
gases are introduced at a specified flow rate into the
reaction chamber; 
  the gas species move to the substrate; 
the reactants get adsorbed on the surface of the
substrate;
the reactants undergo chemical reactions with the
substrate to form the film; and
the gaseous by-products of the reactions are desorbed
and evacuated from the reaction chamber.  

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During the process of chemical vapor deposition, the reactant gases
not only react with the substrate material at the wafer surface (or
very close to it), but also in gas phase in the reactor's atmosphere. 
Reactions that take place at the substrate surface are known as
heterogeneous reactions, and are selectively occurring on the
heated surface of the wafer where they create good-quality films. 
Reactions that take place in the gas phase are known as
homogeneous reactions. 
Homogeneous reactions form gas phase aggregates of the
depositing material, which adhere to the surface poorly and at the
same time form low-density films with lots of defects. 
In short, heterogeneous reactions are much more desirable than
homogeneous reactions during chemical vapor deposition.

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A typical CVD system consists of the following parts: 
 sources of and feed lines for gases;
mass flow controllers for metering the gases into the
system;
a reaction chamber or reactor;
a system for heating up the wafer on which the film is
to be deposited; and
temperature sensors.

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Types of chemical vapor deposition

A number of forms of CVD are in wide use.

These processes differ in the means by which chemical reactions are
initiated (e.g., activation process) and process conditions.
For instance, a reactor is said to be 'hot-wall' if it uses a heating
system that heats up not only the wafer, but the walls of the reactor
itself, an example of which is radiant heating from resistance-heated
coils. 
'Cold-wall' reactors use heating systems that minimize the heating up
of the reactor walls while the wafer is being heated up, an example of
which is heating via IR lamps inside the reactor. 
In hot-wall reactors, films are deposited on the walls in much the
same way as they are deposited on wafers.
so this type of reactor requires frequent wall cleaning.

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Another way of classifying CVD reactors is by basing it
on the range of their operating pressure. 
Atmospheric pressure CVD (APCVD) reactors operate at
atmospheric pressure, and are therefore the simplest in
design. 
Low-pressure CVD (LPCVD) reactors operate at
medium vacuum (30-250 Pa) and higher temperature
than APCVD reactors. 
Plasma Enhanced CVD (PECVD) reactors also operate
under low pressure, but do not depend completely on
thermal energy to accelerate the reaction processes.
They also transfer energy to the reactant gases by using
an RF-induced glow discharge.

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The glow discharge used by a PECVD reactor is created
by applying an RF field to a low-pressure gas, creating
free electrons within the discharge region. 
The electrons are sufficiently energized by the electric
field that gas-phase dissociation and ionization of the
reactant gases occur when the free electrons collide with
them. 
Energetic species are then adsorbed on the film surface,
where they are subjected to ion and electron
bombardment, rearrangements, reactions with other
species, new bond formation, and film formation and
growth.  
Table compares the characteristics of typical APCVD,
LPCVD, and PECVD reactors.

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 APCVD, LPCVD, and PECVD Comparison

CVD Process Advantages Disadvantages Applications

Simple,
Poor Step Coverage,
APCVD Fast Deposition,
Contamination
Low-temperature Oxides
Low Temperature

Excellent Purity, High-temperature Oxides,

Excellent Uniformity, High Temperature,
LPCVD Good Step Coverage, Slow Deposition
Silicon Nitride, Poly-
Si, W, WSi2
Large Wafer Capacity

Low-temperature
Low Temperature, Chemical and Particle
PECVD Good Step Coverage Contamination
Insulators over Metals,
Nitride Passivation

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The range of CVD coatings are diverse and consequently this generates a
wide range of properties as indicated in the following table

CVD Coatings and their properties.

On to various substrates Properties

CVD Coatings
containing

Chromium Solid solution alloys (i) Corrosion / oxidation resistance

(i) with Iron, Nickel and Cobalt (ii) Wear / corrosion resistance
(ii) on Iron as carbides and nitrides

Aluminium As Aluminides with Iron, Cobalt and Nickel High temperature oxidation resistance

Boron As Borides with Iron, Cobalt and Nickel Wear / erosion resistance

Silicon As Silicides with Iron, Tungsten and Molybdenum High temperature oxidation resistance

Titanium As Carbides, nitrides and carbonitride on ferrous and non-ferrous Wear resistance
alloys

Manganese Solid solution alloys on carbon steels Wear resistance

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Advantages of CVD
• Can be used for a wide range of metals and ceramics
• Can be used for coatings or freestanding structures
• Fabricates net or near-net complex shapes
• Is self-cleaning—extremely high purity deposits (>99.995% purity)
• Conforms homogeneously to contours of substrate surface
• Has near-theoretical as-deposited density
• Has controllable thickness and morphology
• Forms alloys
• Infiltrates fiber preforms and foam structures
• Coats internal passages with high length-to-diameter ratios
• Can simultaneously coat multiple components
• Coats powders

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Applications
• CVD processes are used on a surprisingly wide range of industrial
components, from aircraft and land gas turbine blades, timing chain
pins for the automotive industry, radiant grills for gas cookers and
items of chemical plant, to resist various attacks by carbon, oxygen
and sulphur.
• Some important applications are listed below.
• Surface modification to prevent or promote adhesion
• Photoresist adhesion for semiconductor wafers Silane/substrate
adhesion for microarrays (DNA, gene, protein, antibody, tissue)
• MEMS coating to reduce stiction
• BioMEMS and biosensor coating to reduce "drift" in device
performance
• Promote biocompatibility between natural and synthetic materials
Copper capping Anti-corrosive coating

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Physical Vapour Deposition(PVD)
Introduction
1.Physical vapour deposition (PVD) is fundamentally a vaporisation coating
technique, involving transfer of material on an atomic level. It is an
alternative process to electroplating
2.The process is similar to chemical vapour deposition (CVD) except that the
raw materials/precursors, i.e. the material that is going to be deposited starts
out in solid form, whereas in CVD, the precursors are introduced to the
reaction chamber in the gaseous state.

Working Concept
PVD processes are carried out under vacuum conditions. The process
involved four steps:
1.Evaporation
2.Transportation
3.Reaction
4.Deposition
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Evaporation
During 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, ‘vaporising’ them.
Transport
This process simply consists of the movement of ‘vaporised’ atoms from
the target to the substrate to be coated and will generally be a straight line
affair.
Reaction
In some cases coatings will consist of metal oxides, nitrides, carbides and
other such materials.
In these cases, the target will consist of the metal.
The atoms of metal will then react with the appropriate gas during the
transport stage.
For the above examples, the reactive gases may be oxygen, nitrogen and
methane.
In instances where the coating consists of the target material alone, this
step would not be part of the process.

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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.
Fig. shows a schematic diagram of the principles behind one common PVD
method.
The component that is to be coated is placed in a vacuum chamber. The
coating material is evaporated by intense heat from, for example, a tungsten
filament.
An alternative method is to evaporate the coating material by a complex ion
bombardment technique.
The coating is then formed by atoms of the coating material being deposited
onto the surface of the component being treated.

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The vacuum evaporation PVD process

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Variants of PVD include, in order of increasing novelty:
Evaporative Deposition: In which the material to be deposited is heated to a high
vapor pressure by electrically resistive heating in "high" vacuum.
Electron Beam Physical Vapor Deposition: In which the material to be
deposited is heated to a high vapor pressure by electron bombardment in "high"
vacuum.
Sputter Deposition: In which a glow plasma discharge (usually localized around
the "target" by a magnet) bombards the material sputtering some away as a vapor.
Cathodic Arc Deposition: In which a high power arc directed at the target
material blasts away some into a vapor.
Pulsed Laser Deposition: In which a high power laser ablates material from the
target into a vapor.

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 Summary of Merits and Demerits of evaporation methods

Method Merits Demerits

1. high temp 1.  some CMOS processes sensitive
materials to radiation
E-Beam Evaporation
2. good for liftoff 2. alloys difficult
3. highest purity 3. poor step coverage
1. simple to 1. limited source material (no high
implement temp)
Filament Evaporation
2. good for liftoff 2. alloys difficult
3. poor step coverage
1. better step 1. possible grainy films
coverage 2. porous films
2. alloys 3. plasma damage/contamination
Sputter Deposition 3. high temp
materials
4. less radiation
damage
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Importance of PVD Coatings
• PVD coatings are deposited for numerous reasons. Some
of the main ones are:
• Improved hardness and wear resistance
• Reduced friction
• Improved oxidation resistance
• The use of such coatings is aimed at improving efficiency
through improved performance and longer component life.
• They may also allow coated components to operate in
environments that the uncoated component would not
otherwise have been able to perform.

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Advantages
• Materials can be deposited with improved properties compared to the
substrate material
• Almost any type of inorganic material can be used as well as some kinds of
organic materials
• The process is more environmentally friendly than processes such as
electroplating
Disadvantages
• It is a line of sight technique meaning that it is extremely difficult to coat
undercuts and similar surface features
• High capital cost
• Some processes operate at high vacuums and temperatures requiring
skilled operators
• Processes requiring large amounts of heat require appropriate cooling
systems
• The rate of coating deposition is usually quite slow

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Applications
PVD coatings are generally used to improve hardness,
wear resistance and oxidation resistance.
Thus, such coatings use in a wide range of applications
such as:
Aerospace
Automotive
Surgical/Medical
Dies and moulds for all manner of material processing
Cutting tools
Fire arms 3030

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