Methods of fabrication of nano materials

Two approaches – Top Down approach and Bottom Up approach

Top Down Approach

Top-down techniques take a bulk material, machine it, modify it into the desired shape
and product. Classic example is manufacturing of integrated circuits using a sequence of
steps sush as crystal growth, lithography, deposition, etching, CMP, ion implantation etc.

Problems with top down approach

• Cost of new machines and clean room environment grow exponentially with newer
technologies.
• Physical limits of photolithography
• With smaller geometries an conventional materials, heat dissipation is a problem.

Bottom Up Approach
Bottom-up techniques build something from basic materials
– assembling from the atoms/molecules up
– not completely proven in manufacturing yet
Examples:
Self-assembly,Sol-gel process etc.
Advantages
• Allows smaller geometries than photolithography.
• Certain structures such as Carbon Nanotubes and Si nanowires are grown through a
bottom-up process.
• Is more economical than top-down in that it does not waste material to etching.

Fabrication of nano layers

The different techniques involved in the deposition of nano layers are
➢ Physical vapor deposition
➢ Chemical vapor deposition
➢ Epitaxi
➢ Ion implantation
➢ Formation of SiO2.
Physical Vapor Deposition
The physical vapor deposition technique is based on the formation of vapor of the
material to be deposited as a thin film.
The different techniques in PVD are
• Evaporation
• Sputtering Low pressure process
• Ion plating
• Laser ablation

a) Evaporation
This procedure is carried out in a bell jar. A crucible is heated up by a resistance or an electron
gun until a sufficient vapor pressure develops. As a result, material is vaporized and deposited on
the substrate. In resistance heating method, the resistance is wrapped around the crucible, or a
metal wire is heated up by a current and vaporized. If a high vacuum is maintained inside the
chamber, there will be less number of molecules in the chamber and hence the mean free path
will be longer. Hence the evaporated molecule can be deposited on the substrate before striking
an unwanted molecule in the chamber, thereby providing an efficient way of deposition on the
substrate. The rate of deposition can be controlled by the current passing through the filament.

Vacuum system for the vaporization from resistance-heated sources.

 Evaporation by means of electron gun

In the second method, the electron gun (e-gun) produces an electron beam of high energy, e.g.,
10 keV. This beam is directed at the material intended for the deposition on the substrate by
means of a magnetic lens pole arrangement. The energy of the beam causes the material to
evaporate, which is then deposited on the substrate. Since the electron beam falls directly on the
source material, there is no interaction with the chamber. So the incorporation of impurities on
the deposited layer is negligible in this method. Another advantage of electron beam method is
its unlimited supply of evaporating material and applicability of non-conductive or high-melting
materials. But radiation defects in the layer formed may result during the process.

b) Sputtering
In the process of sputtering, an atom or a molecule, usually in its ionized form, hits a solid state
(target) and knocks out surface atoms. This erosion is accompanied by a second process, namely
the deposition of the knocked out atoms on a second solid state (substrate). The different forms
of sputtering are i) glow discharge or DC sputtering ii) High frequency discharge or RF
sputtering and iii) magnetron sputtering.

i) Glow discharge or DC sputtering

This is the simplest form where sputtering is achieved by glow discharge with dc voltage. A
cross section of the arrangement is schematically represented below.

Glow discharge or DC sputtering

After mounting the samples on a holder, the chamber is rinsed repeatedly with Argon gas.
Eventually, a constant gas pressure of some 100 mPa is built up. The target, which is attached a
few centimeters above the substrate, is given a negative dc potential from -500 to -5 000 V,
while both chamber and substrate are grounded. The discharge current requires a conducting
target. When the voltage is slowly increased, a small current flows over the two electrodes. This
current is caused by the ions and electrons which normally appear in the gas and by the electrons
which leave the target after ion bombardment (secondary electrons). Finally a glow discharge
(plasma) of non-reactive ions (Ar) is created inside the chamber. This ions fall on the target
material and break loose cluster of atoms. These atoms are then collected on the surface to be
coated. The resultant film has high purity, greater adhesive strength and homogeneity and also
allows better control of film thickness.

Compound materials can also be deposited using sputtering.Since the different elements of the
compound have different sputtering rates, target stoichiometry is a critical parameter. To deposit
oxide, nitride and carbide thin films, reactive sputtering is used. In reactive sputtering, the
sputtering atmosphere is composed of a mixture of argon and oxygen /nitrogen/hydrocarbon.
Chemical reaction takes place inside the sputtering plasma as well as at the substrate to deposit
the required the thin film.The temperature of the substrate is raised to enhance the reaction.
Deposition time and substrate temperature are the useful parameters to deposit nano structured
materials. Low deposition time will prevent large number of particles from being deposited,
thereby retaining the nano structure. Low temperature of the substrate prevents the
agglomeration of particles.

ii) High Frequency Discharge (RF Sputtering)

DC sputtering is not suitable for depositing insulator materials, because the positive charge on
the target surface, due to the loss of secondary electrons, rejects the ion flux and stop the
sputtering process. RF voltages can be coupled capacitively through the insulating target to the
plasma, so that conducting electrodes are not necessary. During the positive half cycle of the RF
signal, the electrons from the discharge space are attracted to the target, impact on the target and
charge it. Current flow to the RF generator is prevented by the capacitor. During the negative
half-wave of the RF signal, the electrons cannot leave the target due to the work function of the
target material. Thus, the electron charge on the target remains constant.

The ions are subjected to the average electrical field which is caused by the electron charge
accumulated on the target. Depending on the RF power at the target, (the captured charge leads
to a bias of 1 000 V or more) the Ar+ ions will aquire energy within the range of 1 keV and will
hit the target. Thus sputtering occurs. During the first few complete cycles more electrons than
ions are collected at each electrode (high mobility), and cause negative charge to be buildup on
the electrodes. Thus, both electrodes maintain a steady-state DC potential that is negative with
respect to plasma voltage, Vp. The induced negative biasing of the target due to RF powering
means that continuous sputtering of the target occurs throughout the RF cycle. But the wafer
will also be sputtered at the same rate as the target since the voltage drops would be the same at
both electrodes for symmetric system. It would thus be very difficult to deposit any material in
that way.

RF sputter system

To rectify this problem of wafer sputtering, the area of the target electrode is made smaller than
the wafer electrode so that voltage drop at the target electrode will be much greater than at the
other electrode. Hence more Ar+ ions will be attracted towards the target than the wafer so that
almost all the sputtering will occur at the target electrode compared to the wafer.

iii) Magnetron Sputtering

• Plasma generation is an inefficient process and usually less than 0.1% ionization rate is
achieved. Plasma generation can be enhanced by increasing the chamber pressure, but
thius will degrade the film quality. If we can confine the secondary electrons generated
during sputtering process near the catode (target), their high density will increase the
plasma density and make for more efficient sputtering.

A series of magnets with alternating polarity are attached to the back side of the target in a
circular fashion. The magnets create curved magnetic field lines which confine the secondary
electrons to them. The highly concentrated electron gas collides with the ions near the target
and create a denser plasma without the need for higher pressures. Plasma densities can be
increased by two orders of magnitude. This will create erosion rings on the target. This
affects film uniformity and requires frequent replacement of the target. To avoid this oddly
shaped and rotating magnetron rings are used.

c) Ion plating
This process is classed between resistance evaporation and glow discharge. A negative
voltage is applied to the substrate, while the anode is connected with the source of the
metal vaporization. The chamber is subsequently filled with Ar with a pressure of a few
Pa, and the plasma is ignited. After cleaning the wafer by sputtering, the e-gun is
switched on and the material is vaporized. The adhesion and homogeneity of the
compared to a sole PVD. The advantages of ion plating are higher energies of the
vaporized atoms and therefore better adhesion of the produced films. The disadvantage is
heating of the substrate and plasma interactions with radiation-sensitive layers such as
MOS oxides.

Ion Plating System

d) Laser ablation method

A high-energy focused laser beam is capable of eroding the surface of a target rotating
with a velocity of one revolution per second. The material is vaporized on the substrate,
and as a result, a film is produced on it at a rate of 0.07 nm/ laser pulse. The growth can
be supported by heating the substrate (750 °C) and by chemical reactions (oxygen at 50
Pa). Advantages of laser ablation are the deposition of materials of high-melting points, a
good control over impurities, the possibility of the vaporization in oxidizing
environments, and stoichiometric vaporization. A shortcoming is the formation of
droplets on the vaporized layer.
 Laser ablation system

CVD Process
The CVD process is performed in an evacuated chamber. The wafer is put on a carrier and
heated to a temperature between 350 and 800ºC. One or several species of gases are let in so that
a gas pressure is formed between very low and normal pressure. The gas flow hits the wafer at a
normal or a glancing incidence. Now a dissociation (in the case of a single gas species) or
reaction between two species takes place. In both cases, a newly formed molecule adheres to the
wafer surface and participates in the formation of a new layer.
consider silane (SiH4) as an example. On impact, it disintegrates into elementary silicon,
which partly adheres to the surface, and to hydrogen, which is removed by the pumps. The
second case is represented by SiH4, which reacts with N2O to form SiO2.

Poly-Si : SiH4 (g) Si (s) + 2H2 (g)

Si3N4 : 3SiH2Cl2 (g)+4NH3 (g) Si3N4 (s)+6HCl(g)+6H2 (g)

SiO2 : SiH4 (g) + O2 (g) SiO2 (s) + 2H2 (g)

Or

SiH2Cl2 (g)+2N2O (g) SiO2 (s)+2HCl (g)+2N2 (g)

The process can be accompanied other types of gases which act as impurities in the deposited
layer. Examples are phosphine (PH3) or diborane (B2H6), which also disintegrate and deliver
effective phosphorus or boron doping of the deposited silicon.
As the thermal budget gets more and more constrained while more and more layers need to be
added for multi-layer metallization, the temperature for the oxide ( or other) CVD processes
should be reduced. One way for doing this is to supply the necessary energy for the chemical
reaction by ionizing the gas, thus forming a plasma. The major difference to the conventional
CVD is the addition of Ar for the ignition of the plasma and of H2. The most common way to
excite the plasma is the RF field. PECVD is mostly used to deposit dielectrics, and therefore the
DC excitation will not work. The process does not require a deep vacuum, so the reduced
pressure between 50 mtorr to 5 torr is used. The ion density is usually between 109 – 1011 1/cm3
and average electron energies are between 1 to 10 eV. Presence of plasma changes the
thermodynamics of surface reactions and considerably lowers the temperature at which reactions
are possible. For eg, for TiC the deposition reaction is not thermodynamically possible bellow
1218 0K. However, in a presence of plasma, the reaction is possible at as low as 700 0K.

Amorphous or micro-crystalline silicon can be deposited by this method. The degree of the SiH4
content in H2 determines whether amorphous or microcrystalline silicon is deposited. In the first
step, both types are deposited. However, a high concentration of H2 etches the amorphous
portion, and only the microcrystalline component remains. The etching process is even more
favored if higher frequencies.

Schematic CVD reactor geometries for

(a) True vertical reactor
(b) Classic horizontal flow reactor
(c) Modified vertical (or pancake) reactor
(d) Downflow cylinder reactor

Four versions of CVD chamber

 Block diagram of a PECVD system

Advantages of CVD process

• high growth rates possible

• can deposit materials which are hard to evaporate
 • good reproducibility
• can grow epitaxial films
• CVD processes are ideally suited for depositing thin layers of materials on some
substrate. CVD layers always follow the contours of the substrate

Dis advantages
• high temperatures
• complex processes
• toxic and corrosive gasses
• They are generally not suitable for mixtures of materials.

Epitaxi
Epitaxy is the process of depositing a layer on a (crystalline) substrate in such a way that the
layer is also monocrystalline. The layer is often referred to as film. If film and substrate are from
the same material, then it is termed as homoepitaxy (e.g.,silicon-on-silicon), otherwise
heteroepitaxy (e.g., silicon-on-sapphire). Depending on the phase from which the film is made
epitaxy can be classified as vapor phase epitaxy, liquid phase epitaxy (LPE), and solid state
epitaxy. A subclass of vapor phase epitaxy is molecular beam epitaxy (MBE).
The constituents of the deposited film are contained in mini furnaces called Knudsen
cells. During heating some vapor pressure develops and an atom beam is emitted through
successive apertures. The beam hits the wafer surface to which the atoms remain partially
adhered. There, they can react with atoms of a second or third beam, which is also directed
towards the wafer surface. Reaction takes place and finally the film is deposited.The film
deposition depend on the selection of the parameters like wafer temperature, the ratios of the
beam densities, the purity of the surface, etc. The chamber contains many devices like low
energy electron diffraction (LEED), secondary ion mass spectroscopy (SIMS), and Auger and
Raman spectroscopy, for the in situ inspection of the growing layer. The quality of the vacuum is
controlled by a residual gas analyzer.
Kudsen Cell
The material to be deposited is contained in the innermost cell of the which is heated up. Its
temperature is controlled by a set of thermocouples and resistance heaters. The high temperature
may leads to molecular desorption from all warmed up surfaces, to the emission of impurities
into the substrate, and in the worst case, to the breakdown of the vacuum. Therefore, a screen
cooled with liquid air is installed around the internal cell. In order to avoid high thermal flows
between furnace and screen, a water-cooled shield is inserted between them.

Kudsen Cell
Ion Implantation

Ion implantation is a doping technique with which ions are shot into a substrate The desired ion
species is introduced as a gaseous compound through a needle valve. The compound is
dissociated and ionized with an electron beam. The arising ions (including the unwanted ones)
are pulled out of the source area and brought to an energy of 30 keV by a preliminary
acceleration. Then, the ions pass through a magnetic field filter which is adjusted in such a way
that only the desired ion type can run into the acceleration tube. The magnetic field filter is based
on the fact that the Lorentz force for a moving charged particle compels a circular path. The
radius of the circle depends on the magnetic field B, the velocity v, and the mass m of the
particle. More exactly, it depends on m/ e (e is the elementary charge). For the desired ion
species, i.e., for a given m/ e, the magnetic field is adjusted in such a way that the circular path of
these particles terminates exactly at the end of the accelerator tube. There, the ions acquire a total
energy of 360 keV. The beam can be scanned upwards and downwards or left and right, by
means of two capacitor disks. In order to avoid Lissajous figures, different horizontal and
vertical scanning frequencies are chosen. The beam current is measured by an ammeter, which is
connected to the substrate holder isolated against ground. The substrate holder is designed as a
carousel, for implanting several samples without an intermediate ventilation.

Ion Implantation System

Calculation of the Implantation Time

Typical required dose values NI lie between 1012 and 1016 cm-2. The necessary implantation time
depends on the available beam current, I, on the irradiated substrate surface, A, and on the charge
state of the ions. Total charge of the ions implanted during an irradiation time t is Q = q NI A.

𝑄 𝑞𝐴𝑁𝐼
𝑡= =
𝐼 𝐼
Radiation Damage
The penetrating ions pass through the lattice depending on the ion mass/lattice atom mass
ratio and the momentary velocity in a zigzag path. Along this path, the ions impinge on host
 lattice atoms, which leave their places and go to the interstitial site. Thus, lattice defects
of different nature develop. Frenkel defect—is produced by the displacement of a lattice
atom into an interstitial site. Thus, a vacancy and an interstitial atom develop.Vacancies
can possess different charge states (e.g., neutral, positive, negative, double negative).
Furthermore, they can form aggregates with foreign atoms and influence their diffusion.
Double vacancies can be formed if an impinging ion dislodges two nearest neighbor
lattice atoms. or by two single vacancies. Double vacancies are stable up to
approximately 500 K. Dislocations can develop by the association of single defects, or
they grow from unannealed radiation damage into undamaged area during annealing.
Dislocations are areas were the atoms are out of position in the crystal structure.
Dislocation lines anneal only at high temperatures (>1000 °C), and very often they do not
anneal at all in implanted layers. Further defects can be formed by the accumulation of
vacancies and interstitial atoms as well as by the association of foreign atoms with
vacancies or interstitial atoms. If many lattice atoms are displaced by an impact ion in a
considerably small volume, a locally amorphized area develops. This area is known as
cluster. The cluster formation is due to the high mass and energy of the impact particles.
The implanted ion comes to rest usually on an interstitial site after numerous impacts.
Therefore it cannot work as a dopant.

Annealing

Annealing is applied for both the annealing of lattice defects and for the relocation of the
doping atoms from interstitial sites into lattice sites. It is a thermal treatment of the
implanted samples at approximately 900–1100 °C in a suitable atmosphere like nitrogen
or hydrogen gas. The ratio of electrically active ions sitting on lattice sites to the total
number of implanted ions is called activation. Usually, the activation rises monotonously
with temperature. In the case of phosphorus, almost complete activation is achieved at
approximately 700 °C.

Channeling

If the ion beam is shot toward a low indexed crystal orientation, then the ion beam can
runs without resistance through the lattice channels and may reach substantially large
depths. This is known as channeling. Channeling is avoided by tilting the crystal, which
is aligned in (100) direction against the ion beam, usually by 7°. Tilted implant can
produce a doping profile with junction depth that is closer to the theoretical calculations.

Implantation Profile

The distribution of the implants is described by a Gaussian curve.

𝑥−𝑅𝑝 2
−[ ]
∆𝑅𝑝 √2
𝑁(𝑥) = 𝑁𝑚𝑎𝑥 𝑒
 R is the position of the center of the
p
distribution (for the Gaussian curve, ΔR the
p
full width at half maximum of the distribution

The concentration, Nmax , is the maximum of the distribution, calculated from the
implanted doses NI.
∞
∫ 𝑁(𝑥 )𝑑𝑥 = 𝑁𝐼
0

𝑁𝑚𝑎𝑥 ≅ 0.4𝑁𝐼 /∆𝑅𝑝

Formation of SiO2

Oxide layer finds application in wide range of electronic devices. They appear as gate
oxide in MOS transistors, field oxide for isolation purposes, anti-reflection layers in solar cells,
or as passivation layers for long-term protection.

i) Thermal Oxidation
Thermal oxidation can be of two types a) dry oxidation where pure oxygen gas is
passed over the wafer for silicon dioxide formation and b) wet oxidation where
oxygen for oxidation is liberated by passing nitrogen through water.

Si (s) + O2 (g) → SiO2 (s) (dry oxidation)

Or
Si (s) + 2H2O (g) → SiO2 (s) + 2H2(g) (wet oxidation)

Wet oxidation or steam oxidation is a faster process since OH- hydroxyl ions
diffuses faster in oxide layer than dry oxygen. But the later formed will be less dense
than that obtained in dry oxidation. A steam ambient is preferred for the growth of
thick oxides because H2O molecules are smaller than O2 and hence can easily
diffuse through SiO2 , which results in high oxidation rates.

A Si wafer is cleaned so that any organic or heavy metal impurity on the surface
is removed and the natural oxide is dissolved. Then, the wafer is inserted in a quartz
tube heated to a temperature of about 1100 °C. A flow of an oxidizing gas, either
 pure oxygen (dry oxidation) or nitrogen driven through water (wet oxidation), is
maintained. When oxygen penetrates into the substrate, the Si surface reacts with
the oxygen and forms silicon dioxide. This process requires highest cleanliness.

SiO2 Growth Stages

• Carried out in a furnace(quartz

tube) with O2 gas environment
Initi Si (either pure oxygen (dry
al wafer oxidation) or nitrogen driven
through water (wet oxidation))
at about 1100ºC.

➢ Oxygen atoms combine readily

with Si atoms
➢ Linear- oxide grows in equal
Si amounts for each time
Line ➢ Around 500Å thick
wafer
ar

✓ Above 500Å, in order for oxide

layer to keep growing, oxygen and
Si atoms must be in contact
✓ SiO2 layer separate the oxygen in
Parab Si the chamber from the wafer
surface
olic wafer o Si must migrate through the
grown oxide layer to the
oxygen in the vapor
o oxygen must migrate to the
wafer surface
ii) CVD or PECVD
CVD or PECVD techniques can be used for oxide layer deposition. Another version of
CVD process is TEOS deposition. A feed gas (usually nitrogen) is driven through a
container filled with tetraethylorthosilicate (TEOS). TEOS is a liquid at room
temperature. Its chemical structure is

TEOS slowly hydrolyzes into silicon dioxide and ethanol when in contact with ambient
moisture.

Si(C H O) (at 720 °C) = SiO + 2H O + C H .

2 5 4 2 2 2 4

The enriched nitrogen flows to the wafers where SiO2 is deposited on their surfaces.
The deposition is maintained at a temperature of about 650 to 850 °C by means of an
external induction coil. The TEOS is already oxidized, in contrast to the silane process.

TEOS finds only limited application because the deposition temperature (>650 °C)
prevents its use after metallization. In order to obtain lower deposition temperatures,
few molar per cent of ozone is added, which reduces the optimum deposition
temperature to 400 °C.
 iii) Anodic oxidation
In anodic oxidation the wafer is immersed into a 0.04 M solution of KNO3 in
ethylene glycol with a small addition of water. The wafer is mounted on a holder
with a vacuum, and serves as the positive electrode, while a platinum disk acts as a
backplate electrode.

The current causes a reaction on the surface of the silicon.

But the quality of the oxide is too low, and the process is time-consuming or not
compatible with other applications.

iv) Sol gels

In this process, a suspension of oxide particles in an organic solvent is distributed
over the wafer. A centrifuge facilitates homogeneous distribution of the liquid on
the wafer. Then the wafer is baked and the solvent evaporates. The required
temperatures range from 500 to 800 °C. The oxide can have the quality of a gate
oxide.

Fabrication of Nano particles

A nanoparticle is defined as a ball or a ball-like molecule which consists of a few 10 to some
10,000 atoms interconnected by interatomic forces. The deposited nanoparticle layers differ
from uniform layers, particularly due to the presence of grain boundaries, which leads to
different electrical and optical behavior. The synthesized particles should be in nanometric
scale, they should have narrow size distribution and should be pure and homogeneous.

The different processes involved in the synthesis of nanoparticles are

a) Grinding with Iron Balls

This is a mechanical crushing process. The machine consists of special steel balls,few
millimeters in diameter, in a water cooled steel vessel and a high speed motor driving shaft.
The material to be crushed is added in the form of a powder of about 50 µm diameter grain
size. After filling the container with liquid nitrogen, the rotating shaft grinds the material.
The steel balls exert force on the material, the strain is increased, then dislocations are
produced, and finally the dislocations produce new grain boundaries which are smaller than
the initial ones. Thus an increasingly small grain size is achieved. The grinding periods are
within the range of minutes to some 100 hours. The size of the nanoparticles obtained in
the process depends on many factors like type of source material, grinding hour, the weight
ratio of the steel balls to the initial material particles etc. This method is preferred for the
synthesis of metal oxides such as Preferred for the synthesis of metal oxides such as
Al2O3,TiO2 .

Ball mill for fabrication of nano particles

Disadvantages:
o have a relatively broad size distribution
o have varied particle shape or geometry
o may contain a significant amount of impurities from the milling medium
o may contain defects resulting from milling
b) Laser ablation method

Laser beam ablation system

The removal of material from solid surfaces by the technique of laser ablation is known
as laser plume ablation (LPA). The raw material is provided as a solid. Its dissolution is
achieved by a focused laser beam. Deposition takes place in a ultra high vacuum or in
the presence of some neutral gas such as Argon at a certain pressure. The gas at the
desired pressure is used to control the deposition rate as well as film composition. A
high power pulsed laser is focused onto the target material and, when the laser fluence
(power density) exceeds the ablation threshold value for the material, chemical bonds
are broken and the material is fractured into energetic fragments, typically a mixture of
neutral atoms, molecules, and ions. Since these fragments are highly energetic, the
process is considered as an explosive evaporation. Most of the absorbed energy is
deposited in the ejected material, so that there is little or no thermal damage to the
surrounding target material. The vapor (plume) is collected on a substrate placed a short
distance from the target. The advantage of this procedure is a 1:1 transfer of the
material composition from the raw material to the particles.

c) Reduction method
Some metal compounds (e.g., chlorides) can be reduced to elementary metallic
nanopowder by the application of NaBEt3H, LiBEt3H, and NaBH4. The group VI metal
chlorides like CrCl3,MoCl3 when reduced in toluene solution with NaBEt3H at room
temperature gives metal colloids. The reaction is

MClx + x NaBEt3H M + x NaCl + x BEt3 + 2xH2

 When the same metal chlorides are reduced in tetrahydrofuran solution, metal carbides
are obtained.
d) Sol Gel Process
A sol (hydrosol) is a colloidal dispersion in liquid. Gels are formed out of sols due to
condensation reactions as well as van der Waals forces or hydrogen bonds, which let the
particles further grow and cross-link. If the liquid phase of the gels is removed (for
instance by evaporation in vacuum), xerogels are obtained. After removing solvents, the
solid phase network exist which is known as aerogel. The sol/gel transition controls the
particle size and shape.

Sol-Gel process for the production of SiO2:

A catalyst (acid or base) is added to a solution of tetramethoxysilane (TMOS), water,
and methanol.
Step1:
Hydrolysis of the Si–OMe (Me: methyl) bonds leads to the formation of Si–OH groups:
Si(OMe)4 + 4H2O “Si(OH) 4 ” + 4MeOH
Step2:
Further dehydration reduces the “Si(OH)4 ” to SiO2 gel.

Step 3:
Aging of the gel during which polycondensation reaction continue until the gel
transforms into a solid mass (7 days).

Step 4:
Drying of the gel when water and other volatile liquids are removed from the gel
network. ( SiO2 xero gel is formed).During the reaction, the gel reaches a viscosity so low
that it can be applied onto a centrifuge and distributed over the wafer.

Step 5:
Dehydration during which surface bound Me-OH groups are removed. (stabilizing the
gel against rehydration, at about 800°C.

Step 6:
Densification and decomposition of the gels at high temperatures ( > 800°C).

When annealing over 800 °C, homogeneous oxides can be manufactured.

At moderate and low solidification temperatures, the procedure delivers
nanocomposite. By definition, nanocomposites contain nanoparticles of less
 than 1000 nm in a host matrix.

e) Precipitation of quantum dots

❖ Precipitation in glasses

The samples are prepared by high temperature precipitation in molten silicate glass
matrices. After melting, the glass is doped with the desired semiconductor components.
A rapid cooling process is followed by a secondary heat treatment between 600 and
1400°C. Semiconductor crystallites precipitate out of the solid solution. The average
radius of the crystallites is determined by the temperature and duration of the
 secondary heat treatment. This technique is used in the manufacturing of CdS, CdSe,
CdTe, GaAs, and Si nanocrystallites in silica glasses.

❖ Co-deposition of quantum dots with thin films

Common principle is the production of nanocrystallites in a separate step (by

evaporating, laser ablation, sputtering a target, etc.). They are directed towards a
substrate which is, covered at the same time with a film so that they are included into
this film.

❖ By lithography

Since a high resolution is required, electron beam lithography is used. The material
which is to be converted into quantum dots is deposited on a substrate like GaAs via
MBE. The size of the electron beam spot determines the smallest possible size of the
quantum dot. The wafer is etched so that islands of the required size remain. Quantum
dots of a few 10 nm can be produced by the etching process.

f) Self assembly
This phenomenon is usually found in the heteroepitaxy. Three-dimensional islands
are formed with a surprising regularity on a substrate. Due to the free surface energies
(substrate–vacuum, substrate–film, film–vacuum), two extremes can occur: regular
layer-on-layer growth and cluster formation. In the case of a large lattice mismatch, the
film follows a layer-on-layer growth but develops greater and greater pressure. With
sufficient film thickness the film will form three-dimensional islands.

In the case of island formation, the atoms or molecules that are brought on the surface
may do one of the three things

➢ Adsorb and diffuse on the surface until they join or nucleate with another
atom to form an island
➢ Attach themselves to or aggregate into an existing island
➢ Desorb and thereby leave the surface
The small islands can continue to grow, migrate to other positions or evaporate. There is
a critical size at which they become stable and no longer experience evaporation.