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Department of Mechanical Engineering

IV B.Tech I Semester
NANOTECHNOLOGY
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Unit-II
Day - 7
Topics to be covered: Bottom-up and top-down approaches.
1. Explain bottom-up and top down approaches for fabricating of nanostructures with examples.
A. Using the nanotechnology, we can arrange atoms and molecules exactly as we want. In nano
technology, manufactured products are made from atoms. The properties of these products depend on
how the atoms are arranged. For example, if we rearrange the atoms in coal, we get diamond. If we
rearrange the atoms in sand (and add a pinch of impurities), we get computer chips. Two main
approaches are used for the synthesis of nanomaterials and the fabrications of nanostructures in
nanotechnology. They are:
a) Bottom-up approach
b) Top-down approach,
The difference between nanotechnology and conventional technology is that, the bottom-up approach
is preferred in nanotechnology, where as conventional technology usually use the top-down approach.
The difference between two approaches can be explained simply by using a example of powder
production, where the chemical synthesis represents the bottom-up approach while the crushing and
milling of chunks represents the equivalent top-down process. An illustration of the top-down
approach vs. the bottom-up approach is shown in Figure 1.

Fig. 1 Schematic representation of top-down and bottom-up approaches

BOTTOM-UP APPROACH: Bottom-up approach is often emphasized in nanotechnology literature,

though bottom-up is nothing new in materials synthesis. Bottom-up approach refers to the
construction of nanomaterial from the bottom, i.e. atom-by-atom, molecule-by-molecule or cluster-
by-cluster.
In bottom-up approach, the atoms or molecules are used as the building blocks to produce
nanoparticles, nanotubes, nanorods, thin films or layered structures. According to their
dimensionality, these features are also referred to as zero-, one- or two-dimensional nanostructures.

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Following figure also demonstrates the building of particles, layers, nanotubes or nanorods from
atoms (ions) or molecules.

TOP-DOWN APPROACH: The word "top-down" means starting from large pieces of material and
producing the intended structure by mechanical or chemical methods. This situation is shown
schematically in figure. As long as the structure are within a range of sizes that are accessible by
either mechanical tools or photolithography processes, then top-down processes have an unmatched
flexibility in their application.
Top-down is in general an extension of lithography. The principle behind the top-down
approach is to take a bulk piece of the material and then modify it into the wanted nanostructure.
Cutting, grinding and etching are typical fabrication techniques, which have been developed to work
on the nano scale. The sizes of the nanostructures, which can be produced with top-down techniques,
are between 10 to 100 nm.

2. What are the advantages and disadvantages of both methods?

Both approaches play very important roles in modern industry and most likely in nanotechnology
as well. There are advantages and disadvantages in both approaches.
An advantage of the bottom-up approach is the better possibilities to obtain nanostructures with
less defects and more homogeneous chemical compositions. This is due the mechanisms utilized in
the synthesis of nanostructures reducing the Gibbs free energy, so that the produced nanostructures
are in a state closer to a thermodynamic equilibrium.
Top-down approach has proven unsuccessful for several purposes. One of the problems with the
top-down approach is the imperfection of the surface structure. Such defects in the surface structure
can have a significant impact on physical properties and surface chemistry of the nanostructure, since
the surface area to volume ratio in nanostructures and nanomaterials is very large.
The surface imperfection would result in a reduced conductivity due to inelastic surface
scattering, which in turn would lead to the generation of excessive heat and thus impose extra
challenges to the device design and fabrication. Even though there are problems connected to using a
top-down approach, this is the method of choice when highly complex structures are made. This is the
case in the integrated circuit industry, where nano-sized structures are cut in plain silica wafers using
laser techniques.

Day - 8
Topics to be covered: Ball-milling method
3. Explain the ball milling method with neat diagram?
It is one of the simplest ways of making nanoparticles of some metals and alloys in the form of
powder. There are many types of ball mills viz. planetary, vibratory, rod, tumbler etc. A ball mill (a
type of grinder) is a cylindrical device used for grinding (or mixing)
materials to as small as few nanometers.
A ball mill consists of a cylindrical capped container that sits on
two drive shafts (pulleys and belts are used for rotary motion) or
directly connected to motor for rotation. Size of container, of course,
depends upon the quantity of interest. The container is partially filled
with the material to be ground (powder or flakes) plus the grinding
medium (hard spherical balls). Initial material can be of arbitrary size
and shape. Different materials are used as grinding media, including
tungsten carbide balls, ceramic balls, flint pebbles and stainless steel balls.

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Larger balls used for milling, produce smaller grain size and larger defects in the particles. If the
container is more than half filled, the efficiency of milling is reduced.
When the container is rotating about a horizontal axis, the material is forced to the walls and is
pressed against the walls. This internal cascading effect reduces the material to a fine powder. By
controlling the speed of rotation of the container as well as duration of milling, it is possible to ground
the material to fine powder (few nm to few tens of nm) whose size can be quite uniform. This process
may add some impurities from balls. The container may be filled with air or inert gas. However, this
can be an additional source of impurity, if proper precaution to use high purity gases
is not taken.
Some of the materials like Co, Cr, W, Ni- Ti, Al-Fe, Ag-Fe etc are made nanocrystalline using
ball mill. Few milligrams to several kilograms of nanoparticles can be synthesized in a short time of a
few minutes to a few hours.

4. Explain pulsed laser deposition with its schematic layout? List its advantages?
Pulsed laser deposition (PLD) is an efficient method to produce thin films by utilizing a technique
called laser ablation. PLD can be used to deposit a wide range of materials from polymers to metals.
PLD is applicable to almost any material, in particular to compounds (especially multi-element
oxides) that are difficult or impossible to produce in thin-films by other techniques. Examples of such
materials include complex ceramic materials such as hightemperature superconductors and certain
magnetic materials [e.g. yttrium iron garnet (YIG) and ferromagnetic shape-memory (FSM) alloy Ni-
Mn-Ga]. PLD was the first technique used to successfully deposit a superconducting YBa2Cu3O7
thin film.
Typical layout of pulsed laser deposition (PLD) system is as shown in the figure. In general, the
idea of PLD is simple. A high power pulsed laser beam is focused onto the surface of a solid target.
The strong absorption of the electromagnetic radiation by the solid surface leads to rapid evaporation
of the target material. Finally, the evaporated materials get deposited onto the substrate. The
evaporated materials consist of highly excited and ionized species.

Fig. Experimental set-up of PLD.

Factors that influence deposition thickness:
1) Nature of target material.
2) Pulse energy of laser beam.
3) Distance between target to substrate.
4) Type of gas and pressure in chamber (e.g. oxygen, argon, etc.).
Advantages of Pulsed Laser Deposition:

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1) Conceptually PLD is a simple process: a laser beam vaporizes a target surface, producing a film
with the same composition as the target.
2) Cost-effective: one laser can serve many vacuum systems.
3) Fast process: high quality thin films can be grown reliably in 10 or 15 minutes.
4) Films made by PLD can be extremely smooth and amorphous, or crystalline depending on the
chamber atmosphere.
Note: Laser ablation is the process of removing material from a solid surface (or occasionally liquid)
by irradiating it with a laser beam.
Day – 9

Topics to be covered: Thermal evaporation (PVD)

5. Explain thermal/resistive evaporation with its schematic lay out? List the advantages and
disadvantages thermal evaporation?
Thermal/resistive evaporation is a proven and economical method of depositing thin film coatings
in vacuum. Resistive evaporation is used in various applications ranging from decorative coating to
semiconductor manufacturing processes.
Resistive thermal evaporation is one of the most commonly used metal deposition techniques.
Metals such as iron, nickel, aluminum, copper, tin, silver, gold and platinum are frequently deposited
using thermal evaporation methods.

Fig. Experimental set-up of Thermal evaporation.

It consists of vaporizing a solid material (pure metal, eutectic or compound) by heating it to

sufficiently high temperatures and re-condensing it onto a cooled substrate to form a thin film. As the
name implies, the heating is carried out by passing a large current through a filament container
(usually in the shape of a basket, boat or crucible) which has a finite electrical resistance.
The choice of this filament material is dictated by the evaporation temperature and its inertness to
alloying/chemical reaction with the evaporant. Traditionally the filament material is made by tungsten
[W: melting point=3380 °C] or thallium [Ta: M.P=2980°C) or molybdenum [Mo: M.P =2630 °C]
which is with very high melting temperature.
Typical layout of thermal evaporation system is as shown in the above figure
In the thermal evaporation process, the material to be deposited (source material: metal) is
loaded into a container called a crucible which is kept inside a vacuum chamber. The crucible is
resistively heated by passing a high current to a temperature equal to the melting point of the source
material. A high current flowing through the crucible heats it up, melts and causes evaporation of
source material. These vapours of atoms travel in straight lines and they strike the surface of the

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substrate where they accumulate to form a film. This method is useful for depositing many layers of
different materials without chemical interaction between different layers.
Factors that influences the deposition thickness:
1) Pressure inside the vacuum chamber.
2) Temperature of the substrate.
3) Power flowing through the crucible.
4) Distance between source to substrate.
Advantages:
1) Instrumentation is relatively simple and cheap.
2) Less substrate surface damage.
3) Excellent purity of films.
4) Source material (material to be deposited) can be to different shape depending on the need.
Disadvantages:
1) Limited to low melting point metals, e.g.: Al, Au, Ni, Cr…
2) Fit only for metals, the dielectric material is difficult to melt and evaporate to form thin films.
3) The speed of deposition is very slow.
4) The hardness of the film is not good and the density is poor.
5) The materials that deposit on the wall of the chamber can contaminate later depositions.
6) Sometimes there are problems with film-thickness uniformity and uniform doping over large area
substrates.
Day – 10

Topics to be covered: Chemical vapour deposition (CVD)

6. Explain chemical vapour deposition process and growth mechanism with neat diagrams?

Fig. Experimental set-up of CVD

Chemical vapour deposition (a hybrid method using chemicals in vapour phase) is conventionally
used to obtain high purity and high performance coatings of a variety of materials viz. inorganic or
organic materials. It is widely used in industry because of its relatively simple instrumentation, ease
of processing, economical viability and possibility of depositing different types of materials. Under
certain deposition conditions nanocrystalline films or single crystalline films can also be grown.
Basically CVD process can be considered as a transport of reactant vapour or reactant gas towards
the substrate (Fig.) kept at some high temperature where the reactant cracks into different products
which diffuse on the surface (undergo some chemical reaction at appropriate site), nucleate and grow
to form the desired material film. The by-products created on the substrate have to be transported
back to the gaseous phase removing them from the substrate.
Gas or Vapours of desired material may be often pumped into reaction chamber using some
carrier gas (Fig.). In some cases the reactions may occur through aerosol formation in gas phase.
There are various processes such as reduction of gas, chemical reaction between different source
gases, oxidation or some disproportionate reaction by which CVD can proceed.
However, it is preferable that the reaction occurs at the substrate rather than in the gas phase.
Usually temperature ~ 300 to l200°C is used at the substrate and gas pressures in the range of 0.1 torr

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to l.0 torr are used. Growth rate and film quality depend upon the gas pressure and the substrate
temperature.
When the growth takes place at low temperature, it is limited by the kinetics of surface reaction.
At intermediate temperature, it is limited by mass transport, i.e. supply of reacting gases to the
substrate. Here the reaction is faster and supply of reactants is slower. At high temperature, growth
rate reduces due to desorption of precursors from the substrate.
GROWTH MECHANISMS:
When two types of atoms or molecules, say P and Q, are involved in the desired thin film
formation, then there are two mechanisms by which growth can take place.
Langmuir-Hinshelwood mechanism: Both P and Q type of atoms/molecules are adsorbed on the
substrate surface and interact there to produce PQ. When one species is adsorbed in excess of the
other, the growth depends on the availability of adsorption sites for both P and Q as shown in a
schematic diagram Fig.

Fig. Langmuir-Hinshelwood mechanism of growth.

Elay-Riedel mechanism:
One species say Q adsorbs on the substrate and the species P from gas phase interacts with Q.
Thus, there is no sharing of sites. This type of mechanism is known as Elay-Riedel mechanism and is
as shown in Fig.

Fig: Elay-Riedel mechanism of Growth

TYPES OF CVD:
A variety of CVD methods and CVD reactors have been developed, depending on the types of
precursors used, the deposition conditions applied and the forms of energy introduced to the system to
activate the chemical reactions desired for the deposition of solid films on substrates. For example,
when metal organic compounds are used as precursors, the process is generally referred to as metal
organic CVD (MOCVD), and when plasma is used to promote chemical reactions, this is a plasma
enhanced CVD (PECVD). There are many other modified CVD methods, such as low pressure CVD
(LPCVD), laser enhanced or assisted CVD, and aerosol assisted CVD (AACVD).
Day – 11

Topics to be covered: Sol-Gel method

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7. Explain sol-gel process with schematic diagram?
As the name suggests sol-gel involves two types of materials or components, 'sol' and 'gel'. Sols
are solid particles in a liquid (see Fig.). They are thus a subclass of colloids. Gels are nothing but a
continuous network of particles with pores filled with liquid (or polymers containing liquid). A sol-
gel process involves formation of 'sols' in a liquid and then connecting the sol particles (or some
subunits capable of forming a porous network) to form a network. By drying the liquid, it is possible
to obtain powders, thin films or even monolithic solid. Sol-gel method is particularly useful to
synthesize glass materials, ceramics or metal oxides although sulphides, borides and nitrides also are
possible. Nowadays the sol-gel process is quite often used for the fabrication of a variety of
nanomaterials. Usually metal alkoxides and metal chlorides are used as precursors. Figure, shows the
typical sol-gel process.

Fig. Sol-Gel process

Initially, the sol is prepared by dissolve the precursors in solvents. Further, gel is
formed by the process of dehydration. Once the gel is formed there are several ways to convert this
gel to the desire solid form. Depending on the deposition and drying processes or conditions, this gel
can be converted in to various forms such as aerogel, aerogel, gelled spheres, nano powders, nano
wires, nano thin films and dense ceramics.
The first three steps of the figure describe the sol preparation and gel formation. Once the gel is
formed, it can be converted In to aerogel by rapidly drying gel. Also by slow drying process the gel
can be converted in to xerogel, which In turn, can be converted in to small gelled spheres by using
various capping agents, which modify the surface tension of the dispersed particles in the sol and
prevent then from agglomeration. The gelled spheres can be converted in to powders by calcinations.
For nanomaterials fabrication, proper use of surfactants is very important. Because, it controls the
level of agglomeration of the suspended particles in the sol. Therefore, using right kind of surfactants
and proper concentration of surfactants will control the size of the nanoparticles in the powdered
material produced. Another important application of the sol-gel s the formation of nanowires,
nanorods via porous matrix, such as alumina template, porous silicon, etc,.

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The sol is first deposited on the porous matrix, and then by sonication and electro deposition
process the particles suspended in the sol are guided inside the nano-pores of the matrix and then
converted in to nanorod by drying it. Thereafter the porous matrix is removed by some selective
etching process to get free-standing nanorods. Another very important use of sol-gel method is to
deposit thin films on various substrates via dip coating/ spin coating/spraying processes.
For sol-gel dip coating process the substrate is generally dipped in to the sol and taken out to coat
it with required material. Depending on the number of dippings the thickness of the film is
determined. Thereafter, the coated substrate is annealed to get the required film. For spin coating
process the sol is dropped by some arrangement to the substrate followed by spinning of the substrate.
In that way the substrate is coated uniformly and then heated accordingly to get the required film. In
the similar way the spray coating process the sol is sprayed on the substrate to get a uniform coating
and then heated to get the desired film. In all three processes the film thickness, annealing
temperature and annealing time determine the nano crystallinity of the deposited film.
Day – 12

Topics to be covered: Hydrothermal/solvothermal method

8. Explain the growth of various nanostructures by using hydrothermal/solvothermal method?
The Hydrothermal Technique has been the most popular one, gathering interest from scientists
and technologists of different disciplines, particularly in the last fifteen years. The word
“hydrothermal” has geological origin. A self-explanatory word, “hydro” meaning water and
“thermal” meaning heat. It is simply described as the action of water at elevated temperature and
pressure in bringing about changes in autoclave contained chemical solutions with near stoichiometric
ratio.
Hydrothermal solvents have different properties at above 100oC and above 1 atm, especially at
critical point. In order to understand hydrothermal reactions the properties of solvent under
hydrothermal conditions must be known very well. Simply, a chemical synthesis carried out under
high temperature and pressure conditions. The high pressure is normally self-generated from water
vapor (or other chemical solvents, i.e., solvothermal synthesis) at elevated temperatures.
.

Fig. Structure of autoclave

Crystal growth under hydrothermal conditions requires a reaction vessel called an autoclave. In
hydrothermal method highly corrosive salt are used to synthesis inorganic materials for longer reaction
time. The Autoclave must be capable of sustaining highly corrosive solvent at high temperature and
pressure for a longer duration of time. For selecting a suitable autoclave, the first and foremost parameter
is the experimental temperature and pressure conditions and the corrosion resistance in that pressure-
temperature range in a given solvent or hydrothermal fluid. In order for better understanding of
hydrothermal method the following procedure are explain in terms flow chart

An ideal hydrothermal autoclave should have the following characteristics:

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1. Inert to acids, bases and oxidizing agents.
2. It should be easily assemble and dissemble.
3. It should have sufficient length to obtain a desired temperature gradient.
4. It should be leak-proof at desired temperature and pressure.
5. It should bear high pressure and temperature for long duration of time.
Note: If, we used chemical solutions such as ethanol or methanol as a reaction media in the process of
nanostructure growth, it will be considered as a solvothermal method.

Flow Chart for synthesis of CdS: Cu nanostructures.

Day – 13

Topics to be covered: Lithography, photo lithography

9. What is lithography? Explain the basic principle and procedure involved in photo lithography
with neat diagram?
The word lithography has originated from Greek words "litho" (which means stone) and
"gramma" (which means writing). Therefore, lithography literally means carving a stone or writing on
a stone. Now, it is used to mean a process in which a sample is patterned by removing some part of it
(i.e. etching) or sometimes even organizing some material on a suitable substrate. Lithography is very

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extensively used in electronics industry to obtain integrated circuits (IC) or very large scale
integration (VLSI) on small piece of semiconductor substrate often called a "chip".
Common principle in most of the lithography techniques is to expose a material sensitive to either
electromagnetic radiation or to particles at some regions. Such a radiation sensitive material is known
as resist. The selection of area is made using a mask which is transparent in some regions and opaque
in the other regions. This cause’s selective exposure of the resist, making it weaker or stronger
compared to unexposed material depending upon the type of the resist being used. By removing the
exposed or unexposed material in suitable chemicals or plasma, desired pattern is obtained. This may
be done in a number of steps depending upon the pattern and materials involved.

Fig.: Photolithography process steps: (1) surface is coated with metal, (2) coating of photoresist
on the substrate, (3) mask placed over upper layer, (4) exposed to UV radiation, (5) resist
development and striping and (6) etching to get final pattern.

Fig. depicts schematically various steps involved in photolithography to transfer a pattern on the
surface of some semiconductor. A thin film coating of a metal (e.g. chromium) is deposited on a
suitable substrate (e.g. glass or silicon). A positive or a negative photo-resist (usually some polymer)
is coated on metal thin film. Positive photo-resist material has the property that, when exposed to the
appropriate radiation it degrades or some chemical bonds are broken. Negative resist on the other
hand is a material, which hardens (cross-links) on exposure to a radiation. A mask is placed between
the resist coated substrate and the source of light. By using a suitable chemical (developer), the
weakened portion is removed (or image is developed). Remaining unexposed part also can be
removed by appropriate chemical treatment. The remaining material can be dissolved in one step and
the hardened material in another step.
Depending on the radiation used like visible light, X-rays, electrons, ions etc. the lithography
name is tagged with it.
It is possible to use visible, ultraviolet, extreme ultraviolet (EUV) or X-rays to perform
lithography and wherever possible lasers are also used. Highest resolution of the generated features
ultimately depends upon the wavelength of radiation used and interaction of radiation with matter as
well as mask and optical elements used. Smaller the wavelength used smaller can be the feature size
which is limited by diffraction limit, λ/2. Depth of focus depends upon the penetration of incident
radiation. For the lithography using electromagnetic radiation, optical elements and masks have to be
used for various purposes. In the visible range (~700 nm to 400 nm) glass lenses and masks can be
used. In the UV range fused silica or calcium fluoride lenses are used. There are three methods (see
Fig.) viz. "proximity", "contact" and "projection" which can be used to pattern a substrate.
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Fig.: (1) mask is close to the photo-resist, (2) mask is in contact with the resist and (3) focused beam
is scanned through the mask.
As the name suggests, in 'proximity' method, mask is held close to the photo-resist coated
metalized substrate, whereas in 'contact' method the mask is in contact with photo-resist. In both
proximity and contact methods a parallel beam of light fal1s on the mask, which transmits the
radiation through some windows but blocks through opaque parts. Although better resolution is
achieved with contact method as compared to proximity method, in contact method the mask gets
damaged faster. In case of 'projection' method a focused beam is scanned through the mask, which
allows good resolution to be achieved along with the reduced damage of the mask. However,
scanning is a slow process and also requires scanning mechanism adding to the cost.
Day – 14

Topics to be covered: Electron beam lithography

10. Explain electron beam lithography with neat figure?
Figure shows schematically electron beam lithography set up. It is very similar to a scanning
electron microscope (SEM) and requires vacuum (~ 10−5 torr). Sometimes SEM is modified in order to
use it as a lithography set up. Electron beam lithography is a direct writing method, i.e. no mask is
required to generate a pattern. Rather, patterns or masters required for other lithography processes (like
optical lithography and soft lithography) can be generated using electron beam lithography.

Fig.: Electron beam lithography set up.

Electrons with high energy (usually larger than ~ 5 keV) are incident on the photo-resist. Here
also positive or negative photo-resists can be used. Common positive resists are poly-methyl
methacrylate (PMMA) and polybutane-l-sulphone (PBS). Negative resist often used in electron beam
lithography is poly-glycidyl-methacrylate co-ethyl-acrylate (COP). Developers used are methyl-isobutyl-
ketone (MIBK) and isopropylalcohol (IPA) in 1:1 ratio.
A focused electron beam in electron beam lithography is used in two modes, viz. 'vector scan' or
'raster scan'. In vector scan, the electron beam 'writes' on some specified region. After one region is
completed the X-Y scanning stage on which the substrate to be patterned is mounted moves. During its
movement electron beam is put off. Then a new region is selected and 'written' with the beam. This is
continued until whole pattern is generated.
In 'raster scan' the beam is rastered or moved continuously over a small area, line by line. The X-
Y stage of the sample moves at right angles to the beam. The beam is turned off or turned on depending

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upon the pattern. Although very high resolution (~50 nm) is routinely possible using this lithography, due
to scanning mode it is rather slow. For example, if the optical lithography can generate 40 patterns with
1μm resolution in one hour, only five similar patterns would be generated with electron beam. However,
larger layer depth is an added attraction of electron beam lithography as compared to optical beam
lithography.
Day - 15

Topics to be covered:
 synthesis of bulk poly crystalline and single crystalline materials
11. Explain the synthesis of bulk poly crystalline materials?
Generally various types of techniques employed to synthesis of bulk poly crystalline materials,
which has average diameter typically in few micrometers. But practically solid state reaction route is
adopting for make poly crystalline materials. The important parameters that effects the synthesis
mechanism are
(i) The area of contact between the particles
(ii) The rate of nucleation
(iii) The rate of diffusion
The basic steps in a conventional solid state synthesis technique are the following:
(i) Appropriate starting materials are selected with fine grain size to maximize the surface area.
(ii) The starting materials are weighed and mixed together in an agate mortar using pestle.
(iii) The prepared compound is pelletized and sintering in furnace at high temperature.
For example preparation of high temperature superconductor, YBa2Cu3O7 (YBCO), involve multi
steps.
 The step is to mix the powders of the most stable form of the individual cation based compounds.
 The most commonly used powders are Y2O3, Ba2CO3 and CuO that are mixed with proper cation
ratio (1:2:3) and then powder mix is heated at 900oC over the 24 hr followed by slow cooling.
 The resulting compound powder is again ground and the powder reheated to 925 oC over the 24 hr,
this step is repeated to ensure the homogeneity.
 In order to ensure the oxygenation into the lattice the powder sample which compact is heated
following the oxygen 425oC over the 24 hr. at this temperature there is a maximum diffusion of
oxygen in to the lattice.
 Finally the obtained product is considered as YBa2Cu3O7.

12. Explain the synthesis of single crystalline materials?

In general various types of techniques employed to synthesis of single crystalline materials, which
has average diameter typically in few micrometers. The growth of single crystal is tedious process, it
s important for the fabrication of si wafers, si based devices, YIG crystals for solar cells, solid state
lasers and quartz crystal oscillators.

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Czochralski method:

Fig shows the Czochralski single crystal growth setup.

 Single crystals are grown from the melt precursors.
 A tiny crystal seed is required to initiate the growth process.
 At first, the crystal seed of the material to be grown is placed in contact with the surface of the
melt.
 The temperature of the melt is held just above the melting point.
 High viscosity and lower pressure favors the growth mechanism.
 The melt and seed are usually rotate in counterclockwise with respect to the each other.
 Further the seed is gradually pulled out of the melt.
 The melt then solidifies on the surface of the seed.
This process produces high quality crystals. In the case of crystal seed of the given
material is not available; Pt can be used as a seed.
Zone melting method

Fig. Experimental set-up of Zone melting

method
In zone method the thermal profile of the furnace is an important factor. The material is contained
in a boat and only a small region of the charge is melted at any given time. At first only a part of the melt
is in contact with the seed. The boat contained the sample is pulled at controlled velocity through the
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thermal gradient of the furnace. Actually when a particular zone of the material is melted and oriented,
solidification of crystal occurs on the seed. Over a certain time impurities are segregate between melt and
crystal and this phenomenon is basis for the zone refining method for obtain pure single crystals.
Day – 16

Topics to be covered:
 Realizing the semiconductor nanostructures
 Specialized growth techniques for nanostructures
13. Discuss the essentials for realizing the semiconductor nanostructures?
The factors such as size dependence, structure dependence, uniformity, density, confinement
potential are affecting the nanostructures which decide the nature of their applications.
Size and structure dependence:
In most of the semiconductor applications, the electrons and holes are at a lower energy level. The
ratio of the energy separation of the energy states and the thermal energy determine whether the
carriers get thermally excited. The energy level separation should be at least three times of the
thermal energy value (KBT).
As the size of the nanoparticle decreases, the space between energy level increases. This property
determines the optical properties of the nanostructures. Further, the structural properties of
nanostructures determine their optical properties. Most of the radiative processes are diminishes by
the presence of defects in structures, resulting in non radiative processes.
Meanwhile, as the size of the nanostructures increases, the magnetic properties decreases due to
quenching of carrier mobility and consequence surface area.
Uniformity and density of nanostructures:
Uniform nanostructures have small dispersion in shape, size and composition, which are
necessary for semiconductor devices. Besides this the dense nanostructures can increases the
efficiency in certain applications by increasing optical absorption or emission.
Confinement potential
Certain semiconductor applications require effective confinement of electrons and holes in deep
potential wells to avoid the thermal excitation phenomena of carriers at higher temperature. This type
of confinement is found in P-i-N structures. In such structures, a nanostructure is placed with the
intrinsic region of P-i-N structure. This can allow the efficient injection or extraction of carriers.

14. Write a short note on specialized growth techniques for nanostructures

At present synthesis of nanomaterials is one of the most researched fields. It is essential to control
the growth of nanostructures to maximize the effect produced. New techniques, also called as
specialized techniques, are needed for atomic and molecular control of nanomaterials. Advanced
techniques are also preferred for assembling and tailoring of multi function nanomaterials.
Nanostructure growth on modified substrates
In most of the growth techniques, flat substrates are used for growth of nanostructures. This is
because flat surfaces help in the oriented growth of nanostructures. However in certain devices the
surface provided for nanostructures growth consists of stepped surfaces, which are periodic manner.
A periodicity approximately 20 nm in step helps the epitaxial growth and helps in fabrication of
quantum wires.
Fig shows schematic V- shaped grooves with ZnO nanowires arrays on V-grooved Si substrate.
This technique of growing nanowires has to be precisely controlled and can be used to obtain very
thin wires.

Raghu Institute of Technology Dept. of MECH NANOTECHNOLOGY Unit - 2

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In general MBE reactor is used to grow the Semiconductor nanostructures on V-shaped edges
and on cleaved edge surfaces.

Fig. V-shaped
grooves with
ZnO nanowires on V-grooved Si- substrate.

Previous JNTU Questions:

1. List any four bottom up approaches for synthesis of nano powders and explain any one of them in
detail? [8], Set 1, March 2017
2. Define Electro deposition method and explain its principle; Write Advantages and disadvantages
of CVD. [8], Set 1, March 2017
3. Explain Electron beam lithography with a neat sketch. [8], Set 1, March 2017

Raghu Institute of Technology Dept. of MECH NANOTECHNOLOGY Unit - 2